PRÁCTICA 1

Separación de una mezcla de óxidos metálicos y obtención de compuestos

derivados.
1.1.- Separación de una mezcla de óxidos de Cu(II), Pb(II) y Cr(III) [CuO,
PbO y Cr2O3].
1.1.1.- Separación en medio alcalino.
1.1.2.- Separación en medio ácido.
1.2.- Aislamiento del ión Cu(II) en forma de cloruro, CuCl 2, y su uso como
reactivo para la obtención del complejo termocrómico
tetraclorurocuprato(II) de dietilamonio [(C2H5)2NH2]2CuCl4.
1.3.- Aislamiento del ión Pb(II) en forma de PbCl2 y su uso como reactivo
para la obtención de PbO, PbO2 y Pb3O4.
1.4.- Disgregación alcalina oxidante del óxido de Cr(III), y aislamiento en
forma de dicromato potásico (K2Cr2O7).
1.1.- Separación de una mezcla de óxidos de Cu(II), Pb(II) y Cr(III)
[CuO, PbO y Cr2O3].
1.1.1.- Separación en medio alcalino (NaOH).

Se tratan 4.5 g de una mezcla de óxidos (que contiene aproximadamente 2 g de CuO, 2

g de PbO y 0.5 g de Cr2O3), con NaOH 5 M, usando una cantidad diez veces mayor que
la teóricamente necesaria para disolver el óxido de plomo, manteniendo una ebullición
suave durante una hora con agitación y reponiendo agua de forma que el volumen de la
suspensión permanezca prácticamente constante. Se enfría externamente con agua y se
centrifuga inmediatamente (no se debe dejar la mezcla expuesta al aire de un día para
otro: carbonatación). El líquido sobrenadante, que contiene a los iones Pb(II) en
disolución, se separa por decantación y se reserva. El residuo sólido restante, mezcla de
CuO y Cr2O3, se lava una vez con NaOH 1M uniendo las aguas de lavado a la
disolución de Pb(II) anterior y después se lava repetidamente con agua hasta neutralidad
de las aguas de lavado.

Sobre la disolución con contiene los iones Pb(II), se añade gota a gota y con
agitación ácido nítrico concentrado, de forma que se observe la precipitación de
hidróxido de plomo, el pH final debería ser neutro o débilmente alcalino. Si llegara a
ser ácido, rectificar con amoníaco hasta medio ligeramente básico. Esta suspensión se
calienta suavemente para favorecer la floculación del precipitado. Posteriormente éste
se filtra o se centrifuga, se lava con agua y se seca en corriente de aire. El precipitado
obtenido, Pb(OH)2, se reserva para reacciones posteriores (véase aptdo. 1.3).

La mezcla de óxidos de cobre y cromo se trata con H2SO4 1 N, usando un exceso

del 50% sobre la cantidad teóricamente necesaria para disolver el óxido de cobre,
calentando durante aproximadamente media hora y reponiendo agua para mantener el
volumen de la suspensión constante. Se enfría en hielo y se filtra, reservando la
disolución con Cu(II) para su tratamiento posterior. El óxido de Cr(III) aislado se seca
en estufa y se guarda cuidadosamente para reacciones posteriores (véase aptdo. 1.4).

Finalmente, para aislar el Cu(II) de la disolución ácida que lo contiene se añade

poco a poco Na2CO3 (al principio en estado sólido y después, cuando la efervescencia
sea más suave, en disolución concentrada) hasta fuerte alcalinidad y se calienta
suavemente (al calentar el hidróxido puede transformarse en óxido). El precipitado se
lava con agua hasta neutralidad de las aguas de lavado. Seguidamente se redisuelve el
sólido usando HCl 1:1, agitando y calentando hasta su completa disolución. Se evapora
en vitrina hasta un pequeño volumen (procurar no llegar a sequedad) de manera que al
enfriar aparezcan las agujas de CuCl2·2H2O (si se llega a sequedad aparece el
compuesto anhidro de color marrón). Se filtran y se dejan secar en corriente de aire o
depositándolas sobre papel de filtro hasta que éste no se manche (Precaución: utilizar
una espátula de plástico y no una metálica ya que ésta se ataca).

1.1.2.- Separación en medio ácido (HNO3).

Se tratan 4.5 g de una mezcla de óxidos (que contiene 2 g de CuO, 2 g de PbO y

0.5 g de Cr2O3), con HNO3 2 M, usando el doble de la cantidad teóricamente necesaria
para disolver los óxidos de plomo y cobre, manteniendo una ebullición suave durante
una hora con agitación. Durante este tiempo se repone el agua necesaria de forma que el
volumen de la suspensión permanezca aproximadamente constante. Se deja enfriar y se
filtra o centrifuga, lavando el óxido de Cr(III) con agua hasta reacción neutra del agua
de lavado y uniendo a la disolución de Pb(II) y Cu(II) solamente la primera porción del
agua de lavado. El óxido de Cr(III) aislado se seca en estufa y se guarda
cuidadosamente para reacciones posteriores (véase aptdo. 1.4).

La disolución resultante, que contiene a los iones Cu(II) y Pb(II) en disolución

en forma de nitratos, se enfría en baño de hielo y sobre ella se añade la cantidad
estequiométrica teórica de cloruro sódico, disuelta en la mínima cantidad de agua
posible, necesaria para precipitar todo el plomo presente en dicha disolución. Dejar
sedimentar el precipitado resultante y, siempre en baño de hielo, añadir sin agitar unas
gotas de una disolución concentrada de cloruro sódico para comprobar que no precipita
más cloruro de plomo (si se observase precipitación, dejar sedimentar de nuevo y repetir
la operación). Posteriormente se separa el cloruro de plomo por filtración, lavando con
pequeñas porciones de agua/hielo (unir a las aguas madres solamente la primera
fracción de aguas de lavado) y el PbCl2 resultante se deja secar en corriente de aire. Se
puede tratar de obtener más cloruro de plomo concentrando la disolución y enfriando a
cero grados.

Finalmente, se procede a aislar el Cu(II) de la disolución ácida que lo contiene.

A pesar de todas las precauciones tomadas, esta disolución puede aún estar contaminada
por iones Pb(II) en disolución, para confirmar o no esto último, se añaden unas gotas de
KI, si se forma un precipitado de color naranja (PbI2 mucho más insoluble que el PbCl2)
se añade más KI hasta que no se forme más PbI2 y éste se separa por filtración o
centrifugación. A la disolución que contiene los iones Cu(II) se añade poco a poco
Na2CO3 (al principio en estado sólido y después, cuando la efervescencia sea más
suave, en disolución concentrada) hasta fuerte alcalinidad y se calienta suavemente (al
calentar el hidróxido puede transformarse en óxido). El precipitado se lava con agua
hasta neutralidad de las aguas de lavado. Seguidamente se redisuelve el sólido usando
HCl 1:1, agitando y calentando hasta su completa disolución. Se evapora en vitrina
hasta un pequeño volumen (procurar no llegar a sequedad) de manera que al enfriar
aparezcan las agujas de CuCl2·2H2O (si se llega a sequedad aparece el compuesto
anhidro de color marrón). Se filtran y se dejan secar en corriente de aire o
depositándolas sobre papel de filtro hasta que éste no se manche (Precaución: utilizar
una espátula de plástico y no una metálica ya que ésta se ataca).
1.2.- Aislamiento del ión Cu(II) en forma de cloruro, CuCl2·2H2O, y su
uso como reactivo para la obtención del complejo termocrómico
tetraclorocuprato(II) de dietilamonio [(C2H5)2NH2]2CuCl4.
El CuCl2·2H2O obtenido tras la etapa de separación se va a utilizar como
producto de partida para la obtención de un complejo metálico de Cu(II) termocrómico,
esto es, que cambia su color en función de la temperatura a la que se encuentra. El
cloruro de cobre obtenido puede presentar un color que varíe entre el verde y el celeste
dependiendo fundamentalmente del tamaño de los cristales. Igualmente puede estar
contaminado con NaCl que es importante eliminar. Para corroborar esta contaminación
se puede disolver un poco del producto obtenido en etanol, si existe contaminación de
NaCl, éste no se disolverá.

- Obtención de cloruro de dietilamonio.

Se mezcla la cantidad apropiada de dietilamina con un volumen igual de agua. A

esta disolución se le añade poco a poco y con agitación (reacción exotérmica) la
cantidad estequiométrica de HCl concentrado. Al acercarnos al punto de equivalencia,
la adición de HCl se hará de manera cuidadosa y controlando el pH, hasta que éste vire.

La disolución se concentra hasta un pequeño volumen de forma que al enfriar se

forme una masa de cristales (si esto no ocurre, se evapora un poco más). Esta masa se
filtra en Büchner, se redisuelve en la menor cantidad posible de etanol y el producto se
precipita añadiendo éter. Se filtra, se seca con un poco más de éter y se recoge
rápidamente en un tubo de ensayo seco previamente pesado que se cierra a continuación
(producto muy higroscópico).

- Obtención del complejo tetraclorurocuprato(II) de dietilamonio.

Se mezclan disoluciones etanólicas de cloruro de cobre y cloruro de dietilamonio
en proporciones estequiométricas. Se evapora hasta que quede un pequeño volumen y se
enfría de manera que se obtenga el producto en forma de agujas verdes. La
cristalización es difícil y a veces se forma un aceite viscoso, en estos casos se puede
ayudar a la cristalización sembrando semillas del producto ya formado o bien raspando
enérgicamente con una espátula en el fondo del vaso o del vidrio de reloj.

Tomar unos cuantos cristales verdes del producto final y colocarlos en un tubo
de ensayo. Introducirlo en baño maría y observar el cambio de color.
1.3.- Aislamiento del ión Pb(II) en forma de PbCl2 y su uso como
reactivo para la obtención de PbO, PbO2 y Pb3O4.
El PbCl2 aislado previamente se redisuelve en la mínima cantidad posible de
agua caliente y se transforma en hidróxido (Pb(OH)2) añadiendo una disolución de
hidróxido amónico hasta fuerte alcalinidad. El Pb(OH)2 obtenido se filtra, se lava con
agua y se seca en corriente de aire. El total obtenido se divide en tres partes iguales cada
una de las cuales servirá para la obtención de los óxidos de plomo que se indican a
continuación.

- Obtención de óxido de plomo(II),PbO.

El Pb(OH)2 se transforma en PbO por simple calentamiento en estufa a 100ºC

durante varias horas.

- Obtención de óxido de plomo(IV), PbO2.

12 g de PbO se suspenden en 50 mL de agua y se trata con una disolución que contiene

10 g de NaOH en 90 mL de agua. Sobre la disolución resultante se agregan poco a poco
y con agitación 80 ml. de una disolución de hipoclorito sódico. Se calienta y se
mantiene a ebullición durante unos minutos. Se deja sedimentar el dióxido de plomo
formado y se prueba si la oxidación ha sido completa añadiendo unas gotas de
hipoclorito al líquido sobrenadante (si se forma más precipitado, añadir más hipoclorito
sódico y volver a calentar). El precipitado se separa y lava por decantación, primero tres
veces con agua, después una vez con 50 mL de HNO3 3M (para eliminar el Pb2+ que
pueda quedar) y después de nuevo con agua, finalmente filtrándose y lavando en filtro
hasta neutralidad de las aguas de lavado. El producto se puede secar en estufa.

- Obtención de minio, Pb3O4.

Se obtiene calentando en presencia de aire óxido o carbonato de plomo a 460ºC.

También se puede obtener por reducción del dióxido de plomo. En ambos casos,
simplemente se deja en un horno a esa temperatura durante varias horas.
1.4.- Disgregación alcalina oxidante del óxido de Cr(III), y aislamiento
en forma de dicromato potásico (K2Cr2O7).
- Disgregación alcalina oxidante del óxido de cromo.

En este proceso de disgregación, el Cr2O3 previamente aislado se va a oxidar a

cromato, CrO42-. Se pesa el Cr2O3, previamente secado en estufa, y se mezcla con 5
veces su peso de nitrato potásico y 4 veces su peso de hidróxido potásico, molturándose
finamente. Se lleva a un crisol y se calienta enérgicamente hasta que la mezcla funda
por completo, manteniéndose fundida durante unos minutos. El calentamiento se puede
realizar mediante sopletes o, alternativamente, se puede introducir el crisol en un lecho
de grafito y someterlo a radiación de microondas. En este último caso, se programa el
horno de microondas a 800 W, calentando durante periodos consecutivos de veinte
segundos, abriendo el microondas y girando el contenedor mediante unas pinzas entre
un periodo y otro. En el caso de que se estén desprendiendo burbujas de gas, esperar a
que cese el desprendimiento antes de volver a aplicar la radiación.

Se deja enfriar a temperatura ambiente. Si el crisol está manchado externamente

con grafito, límpiese bien para no contaminar la muestra. Se trata la mezcla con agua
caliente filtrando el Cr2O3 que no haya reaccionado. Se obtiene una disolución amarilla
de cromato.

IMPORTANTE: PRECAUCIONES AL USAR EL HORNO DE MICROONDAS

Se está utilizando un horno de microondas en unas condiciones diferentes a aquellas para las que fue

diseñado, por tanto deben extremarse las precauciones en su uso.

- No debe utilizarse durante más tiempo ni a más potencia de la indicada en la receta. No conectar nunca

en vacío. No conectar nunca el grill si el aparato dispone del mismo.

- Alguien debe permanecer siempre junto al aparato mientras está funcionando comprobando que no

ocurre nada anormal. En caso de cualquier tipo de incidencia (olores, humo, chispas, etc.) se debe

desconectar inmediatamente el horno poniendo el reloj a cero o abriendo la puerta. Desenchufar de la

pared y avisar al profesor.

- El contenedor de grafito y el crisol alcanzan temperaturas extremadamente altas, se deben utilizar

pinzas para sacar el contenedor del horno y para sacar el crisol del contenedor y no se deben tocar con

las manos hasta que se hayan enfriado a temperatura ambiente.

- No usar nunca para otro fin que el indicado. En particular no introducir ningún sistema que pueda

emitir ninguna sustancia corrosiva en estado gaseoso.

- En ningún caso se debe realizar este tipo de experiencias en el microondas de casa.

 - Aislamiento del cromo en forma de dicromato potásico.

Se trata la disolución amarilla que contiene cromato con ácido acético

glacial hasta alcanzar un pH cercano a 6. Se hierve la disolución para eliminar el exceso
de CO2 generado y se comprueba el pH asegurándonos que no es demasiado básico. A
la disolución se le añade un ligero exceso de nitrato de bario disuelto en la mínima
cantidad de agua, apareciendo un precipitado de cromato de bario (BaCrO4). Este
precipitado se separa por filtración o centrifugación y se lava repetidas veces con agua
El sólido se seca en estufa y se pesa. A continuación se somete a un proceso de
digestión durante al menos una hora con la cantidad estequiométrica de
hidrógenosulfato de potasio disuelto en agua. Se separa por filtración o centrifugación el
sulfato de bario generado, evaporándose la disolución hasta un volumen mínimo (sin
llegar a sequedad). Al enfriar debe cristalizar el dicromato potásico, K2Cr2O7, en forma
de agujas de color naranja.
 PRÁCTICA 2
Síntesis y caracterización del compuesto trans-
[Co(en)2Cl2]3[Fe(ox)3]·4.5H2O
1.1.- Síntesis del complejo metálico trisoxalato ferrato potásico,
K3[Fe(C2O4)3]·3H2O..
1.2.- Síntesis del complejo metálico cloruro de trans-
diclorurobis(etilendiamina)Cobalto(III), trans-[Co(en)2Cl2]Cl.
1.3.- Síntesis y caracterización de una sal mixta de Fe(III)- Co(III)
trisoxalatoferrato de trans-diclorurobisetilendiaminacobalto(III)
tetrahemihidratado, trans-[Co(en)2Cl2]3[Fe(ox)3]·4.5H2O.
1.1.- Síntesis del complejo metálico trisoxalato ferrato potásico,
K3[Fe(C2O4)3]·3H2O..

4 g de BaCl2·2H2O (16.4 mmol) se disuelven en 20 mL de agua y se mezclan

con una disolución de 3.2 g de K2C2O4·H2O (17.3 mmol) en 16 mL de agua,
calentándose a unos 70ºC. La mezcla se enfría y se filtra y el precipitado se lava tres
veces con 3 mL de agua. A continuación se suspende en 50 mL de agua que contenga 2
g de sulfato férrico (5 mmol) y 1.9 g de K2C2O4·H2O. Toda la mezcla se somete a
digestión en baño de agua durante tres horas en ausencia de luz directa y agitando de
vez en cuando. El sulfato de bario precipitado se separa por filtración y se lava con 4
mL (aprox) de agua caliente; el filtrado y el agua de lavado se mezclan y, en ausencia de
luz, se reduce el volumen en baño de agua hasta un volumen aproximado de 8 mL y se
enfría en hielo para lograr la cristalización. Los cristales verdes amarillentos se desecan
en la oscuridad una vez filtrados. Tanto el sólido como la disolución acuosa son
inestables a la acción de la luz directa, depositándose oxalato ferroso de color amarillo.
El complejo es una mezcla de las formas dextrógira y levógira, las cuales se ha logrado
obtener aisladas.
1.2.- Síntesis del complejo metálico cloruro de trans-
diclorurobis(etilendiamina)Cobalto(III), trans-[Co(en)2Cl2]Cl.

A una mezcla de 5.2 g de etilendiamina anhidra en aproximadamente 50 mL de

agua se le añaden una disolución acuosa de CoCl 2·6H2O (10 g) en aproximadamente 40
mL de H2O. La solución resultante, de color rojizo se pasa a un matraz de succión de
250 mL (Kitasatos) provisto de un tapón y de un tubo para entrada de gas cuyo extremo
se encuentre casi en el fondo del recipiente. Se hace pasar una corriente vigorosa de aire
a través del líquido durante 3 horas; la mezcla adquiere un color rojo rubí oscuro.

La disolución oxidada se coloca en un recipiente ancho y se agregan 30.2 mL de

HCl(conc), evaporándose hasta un volumen de 50 mL (aprox.). Al enfriar a temperatura
ambiente cristaliza el producto trans-[Co(en)2Cl2]·HCl·2H2O en forma de láminas. El
producto se deja escurrir sobre filtro. Enfriando en hielo las aguas madres se puede
obtener otra fracción de producto así como evaporando posteriormente hasta 300 mL, si
bien estas fracciones tienen cada vez más posibilidades de estar impurificadas por
[Co(en)3]Cl3·3H2O (color amarillo) y (enH2)Cl2 (incoloro).

Los cristales verdes se molturan en un mortero con EtOH eliminando así el HCl y
el H2O de cristalización obteniéndose la sal anhidra.

- Obtención del isómero cis-[Co(en)2Cl2]Cl

Una pequeña fracción del compuesto obtenido anteriormente se puede transformar

en el isómero cis, de un intenso color violeta¸ disolviéndola en la mínima cantidad de
agua, calentando a 90 ºC al baño maría hasta alcanzar casi sequedad y repitiendo varias
veces este proceso hasta completa isomerización.

Es posible obtener de nuevo el isómero trans añadiendo al medio ácido

clorhídrico y calentando de nuevo.
1.3.- Síntesis y caracterización de una sal mixta de Fe(III)- Co(III)
trisoxalatoferrato de trans-diclorurobisetilendiaminacobalto(III)
tetrahemihidratado, trans-[Co(en)2Cl2]3[Fe(ox)3]·4.5H2O.

La síntesis y caracterización de este complejo se llevará a cabo siguiendo los

procedimientos descritos en el artículo J. Chem. Ed., 63(10), 1986, 902-904.
Complete Characterization of
tran~-[Co(en)2C1~]~[Fe(ox)~] 45H20
An Extended Undergraduate Project Involving an Unknown Metal Complex
Graham S. Bull and Graeme H. Searle
Universlty of Adelaide, Adelaide, South Australia 5001, Australia
In a previous article we briefly reviewed project experi-
ments involvine the complete characterization of "un-
known" inorganic compouuds ( I ) . In these projects the com-
pounds are of unknown formulation (although the constitu-
ents are presumed to be known, either from the synthetic
procedure or from information provided), and from the re-
sults of various analyses and measurements the formula-
tions and geometrical structures are required to he deduced.
Such experiments require a more critical interpretation of
experimental results than the more usual experiments in-
volving known compounds and require the integration of
results from a variety of techniques. Relatively few such
exoeriments seem to be available. and our orevious article
descrihed projects with unknown complexes containing the
labile comolex inns ICnC1,I2- and ICuCLl' .
We no; describe'an eGended project of the same type
employing the combination complex compound trans-
.
[Co(en)2Cl2]3[Fe(ox)3] 4%H20 (en = ethane-1,2-diamine,
ox = C Z O ~ ~which
- ) , has been specifically devised. This com-
pound: denoted X, contains six dift'e;ent components in
both inert and lahile contplex ions, and it thus provides for a
variety of measuremmts. The individual experiments in the
proiect include ion-exchangr separarions of the component
ioniplex ions, qualitative chemical tests for the components
in each complex ion, analyses for all the components, and
various nhvsical measurements. The individual oarent com-
plexes trans-[~o(en)~~l~]~1(2-4) and ~ ~ [ ~ e ( o..Hz0
x j ~ ](2,
5-10) have been popular in undergraduate synthesis and
characterization experiments, and the new project incorpo-
rates some of these characterizations.
Our full projrct is assigned to small numhers of our ad-
vanrrd students (final yrar HSr) working in pairs, and re-
quires two full days. Thecompound X i s prepared by lahora-
tory staff, and th? studenu are provided with samples as an
"unknown", though with the six components specified. The
two students apportion the various separate experiments
and collate and interpret the results collaboratively. They
are required t o show how the formulation and structure of X
are deduced from the exoerimeutal results and to account
for and explain all their bhservations and quantitative re-
sults from the various determinations on the basis of the
deduced structure.
Information Provlded
About 5.0 g of comoound X is provided for each determi-
nation (studint air): T h r com~bnentsare given as Fe, Co,
CI, ox", en, and H20, hut the oxidation states of the metals
are not specified. The proportion of hydrate water (as deter-
mined by weight loss at 100 OC) is provided (6.9% wlw) to
avoid any uncertainty in the water mole ratio which is nouin-
tegral (H20/Fe = 4.5). The compound X is stated to be
moderatelv soluble in water and conductine. indicatine it to
be "ionic': This and the presence of the t& metals sLould
--
sueeest the likelihood of two different c o m ~ l e xions in X.
This problem is more complicated than previous "unk-
nowns", so that we prescrihe the various experiments to he
carried out and give some guidance for the methods and
quantities of materials to be used.
902 Journal of Chemical Education
In our instructions i t is suggested that the following char-
acteristics for the compound he considered and that the
various possibilities he progressively limited as the experi-
ments proceed.
1) The likely oxidation states for the two metals. (These are Limited
to +2 and +3 with the possible Ligands).
2) The possibilities of high- and low-spin configurations for each
metal ion.
3) l'hr po~siblenurnhers of unpaired el~ctrons.
4 ) The posrilditier of the complex ions hemg inert or labile.
51 How,ronsequently.X might observably renrr with acid or alkali.
Knowledge of the empirical formula and formula weight
are required for interpreting the tests and calculating some
-
of the results (conductance.. maenetic moment. and ion ex-
change), so that it is advantageous that the'analyses be
com~letedfirst. Students may be unfamiliar with multicom-
plex-ion compounds so that we indicate the formula weight
range (1000-1400). However, the correct formula weight
should emerge without difficulty from the analysis results,
even allowing for errors of about 5% in each analysis.
The project involves the following 10 experiments.
1) Separatlon of the Component ions Uslng Ion Exchange
Separate solutions of X (0.1 g in 10 mL of water) are
passed through small columns of cation-exchange resin
(Dowex 50W-X2, 200-400 mesh, Na+ form; regenerate the
resin with 1 M NaOH, then wash until the effluent is neu-
tral) and anion-exchange resin (Amberlite IRA-400, NO3-
form; regenerate the resin with concentrated H N 0 3 until
free of C1-, then wash until the effluent is neutral). Columns
1.2 cm diam X 4 cm long of wet-bed resins are suitable. The
respective effluents contain Na3[Fe(ox)s] (pale green-yel-
low) and trans-[Co(en)zC12]N03 (deep green), and are col-
lected for measurements (2) and (3) below.
2) Vlslble Spectra
The visible spectra of these solutions are measured as
obtained from the columns (neutral solutions) and are re-
measured after acidification a s a test for lability (afew drops
of concentrated H N 0 3 are added to each solution cell). The
spectrum of the green complex cation shows onevisible band
a t 617 nm, and this is essentially unchanged with HN03,
suggesting an inert complex (Co(II1)). The spectrum of the
oale ereen-vellow comolex anion shows no hands in the visi-
ble, and the color is evidently due to charge-transfer absorp-
tion extending into the visible with a shoulder a t 455 nm.
With H N 0 3 the color becomes more intense yellow immedi-
ately, indicating a labile complex, and the shoulder disap-
pears. (The absorbing species is now essentially Feaq3+).
These characteristics might suggest that the anion is a d5
high-spin system, and hence is Fe(II1).
3) Qualitative Tests to Determine the Components
in Each Ion
The following qualitative tests should provide informa-
tion on the disoositions of Fe. Co. ox2-, and C1- hetween the
two complex ions, on the oxidation states of the metals, and
on the labile or inert character of each complex ion.

Add NaOH. Red-brown,dirty green, or blue precipitates indicate
Fe(III), Fe(II), or Co(II),respectively. No precipitate suggests an
inert complex.
Fdl0 and/or o$
Add HISO,. A n immediate color change indicates a lahile cum-
plex. Warm and add KMnO, dropwisp, when decolorination indi-
cates Frtll) andlor 0x2-, and C02huhhles indicate ox2-.
Oxalate in the Presence of Fe(l0
Add NaOH, and filter off any hydroxide precipitate. To the fil-
trate add HzSOa and KMnOd. Decolorization and COz bubbles indi-
cate ox2-.
Chlorlde
Add HNOx.. (an
. immediate color chanee indicates a labile eom-
plev and AgNO,. An immediate white precipitate shows Weither
ionic or fnm a lalde complex. A precipitate appearing on warming
suggrsls hvdrolv~i~uf C1- from an inert complen.
Oxalate ff Chloride is Absent
Add AgN03. An immediate white precipitate of Agzoxshows 0x2-
either ionic or from a lahile complex. Agzox is confirmed by its
solubility in HN03.
Fe(lN), Fdl0, or Call)
Add HzSOI, then KSCN. A deep red color shows Fe(III), con-
firmed by decolarizatian with SnClz; no color suggests Fe(II), con-
firmed by the temporary appearance of red Fe(II1)with HzOz;apale
pink-mauve color suggests Co(l1).
Add H2SOCthen KSCN. A deep red color shows Fe(III),which is
confirmed by decolorization on adding NHIF solid.
can)
Add H2SOs then KSCN solid. A mauve solution indicates Co(I1).
(Add NHaF solid to remove Fe(II1) if present). Add amyl alcohol,
when deep blue Co(II) extracts into the alcohol layer.
CdNI), if Co(l0 is Absent
Add H&Oc then SnCln and warm. A gradual change to pink
suggests Co(II1) is being reduced, confirmed on addition of KSCN
solid and amyl alcohol.
These tests should show that the pale green anion is lahile
and contains Fe(II1) and ox2-. The green cation is shown to
be inert and to contain Co(II1) and coordinated Cl-. This
halide hydrolyzes slowly in acid and rapidly with NaOH.
4) Analysls for Coban
Cobalt may he determined by atomic absorption a t 304.4
nm. Assume 10-20% wlw cobalt in the compound.
5) Analysis for Chloride
Transfer asample of X (0.2-0.3 g, accurately weighed) to a
250-mL heaker. Add 30 mL of 1M NaOH and antibumoine
granules, and heat the solution a t just below boiling for 5
min. Cool, add 30 mL of 2 M HN03, and add water to adjust
the volume to about 120 mL. Titrate the solution potentio-
metrically with standard 0.05 M AgN03, with the solution
stirred magnetically.
6) Analysis for Oxalate and Iron
A solution of X in water (about 0.6 g in 30 mL) is passed
throuah a column (1.2 cm diam X 5 cm lone. wet-bed) of
ow ex 50W-X2 cation-exchange resin, 200-400 mesh, inthe
Na+ form. The cation is retained. and the total effluent olus
'washings (until the effluent becomes colorless) is collected in
a titration flask, H2SOl is added (25 mL of 2 M), and the
solution is titrated.with standard 0.02 M KMn04.
Zinc powder (2 g) is then added t o the flask and contents,
and the solution is maintained a t just below hoiling for 10
min. After cooling, the solution is filtered through sintered
glass (washing with 2 M HzS04). then is titrated again with
0.02 M KMnO*. The first titer corres~ondsto the ox2- con-
tent [plus Fe(fI) if it were present] A d the second titer to
total Fe, and the theoretical ratio of the titers is 6.
Titrations of the 0x2- and Fe(I1) directly on a solution of
the total compound proved unreliable due t o color interfer-
ences by the complex cation and Co(I1) in the two titrations,
res~ectivelv.The above orocedure confirms that the Fe and
oxi- are hoih in the com&ex anion.
7) Analysls for Ethane-1,2-dlamlne
This may he carried out by decomposing the complex with
sodium sulfide, then removing the en in a continuous distil-
lation with toluene, as described previously (11).About 0.3 g
of X should he used.
The analytical results for all the components may he cal-
culated both as % wlw (to check their total) and as mole of
component per gram of X. The mole ratios of the compo-
nents are then calculated as multiples of the lowest value (Fe
= I), and give the empirical formula of the compound as
FeCo3Cken~ox3(H20)~ ~,z.Theformula weight can then be
calculated (FW = 1151).
8) Conductance
Using the formula weight determined as above, solutions
in water ol0.016,0.008,0.004, and 0.001 Mare prepared, and
the ronductanres at 25 'C are measured. From a plot of A,.
versus (concentration)'/2, the molar conductance it infinite
dilution A,0 is estimated, and hence the number of charge
units per formula weight is deduced.
The Am0ohtained is about 420 ~hrn-'cm~mol-~, indicating
six charge units ner formula weieht. This information to-
gether with the pievious results eiahles X t o he formulated
as [CO(III)]~[F~(III)]~-.
9) Magnetlc Moment
The magnetic moment is determined by the Gouy method
usina the calculated formula weieht.
~ 6 p.nohtained,
e around 6.0 B~M.,indicates five unpaired
electrons per mole, and this is consistent only with Fe(II1)
high-spin and Co(II1) low-spin.
10) Displacement of CI- by Anion Exchange
Prepare a column (1.2 cm diam X 5 cm long, wet-bed) of
Amherlite IRA-400 anion-exchange resin, C1- form, and
wash the column with water until the effluent is free of C1-.
Pass a solution of X in water (use 0.15-0.20 e) slowlv
through the column, and collect thekffluent and wishings i;
a beaker until essentially all displaced C1- has been removed
from the column. Hydrolyze this effluent with NaOH (as
with the chloride analysis above), then acidify with HN03.
Titrate the solution potentiometrically with standard 0.05
M ApNOx. Determine the number of moles of CI- disolaced
per mole of compound, and interpret this result.
Nine moles of CI- per mole of compound are displaced
(experimental 8.3). ~ h e s arise
e as three displaced by the 3-
anion and six hydrolyzed from the green cation that had
passed through the column unchanged. Evidently the
[Fe(0x)~]3-ion has high stability' since it does not apprecia-
hlv dissociate on the column: such dissociation would eiveu
six CI- displaced by three ox; dissociated.
All the information obtained allows X to be formulated as
[C0(en)~C1~]~[Fe(ox)~] . 4SH20. Finally, the isomer of the
cobalt(II1) complex cation is identified as trans by its green
color.
' Ka is about 4, B3 about 20.
Volume 63 Number 10 October 1986 903

This is a challenging project, in which students have to
adapt their experience with measurements on simpler or
known complexes previouslv to a new situation. It also draws
on students' knowledge of the various features and types of
behavior of transition metal complexes, such as high- and
low-spin configurations, labile and inert complexes, and
thermodynamic stability, and the various possibilities are
required to be matched with the experimental results ob-
.-- --- -.
tained
Other educative features of the experiment include the
following. The students can appreciate in a first-hand man-
ner how a variety of measurements may have to he applied t o
a prohlem if i t is "unknown", as in real research situations.
The necessity for such internation of measurements mav not
he evident in the more usual undergraduate experiments
with inorganic compounds (2,6,12.13) in which svnthesized
or "known" comp&nds are characterized only by selected
analyses or measurements. The usefulness of ion-exchange
operations in manipulating complexes in aqueous solution, a
technique infrequently incorporated in experiments in the
texts (14,15), is well demonstrated in this project. The nec-
essary role of chemical tests (2, 6, 12) in investigating un-
known compounds is also made apparent, whereas contem-
porary courses seem to have decreased emphasis on qualita-
tive analvsis.
The pioject has been developed to provide the maximum
benefit in its "unknown" format. However. i t could be ab-
breviated if the formula or structure of the'compound were
partly or wholly provided, and students could then be re-
quired to demonstrate how the results of selected measure-
ments are consistent with the information eiven. Such an
abbreviated format could provide instructivi and interest-
ing work for less advanced students.
Extended projects of this same type could be devised with
other combination complex compounds. Some readily oh-
tained complex ions, all with simple ligands, that could he
incorporated are the following: [Ni(en)J2+, [Al(o~)~]3-,
[Cu(ox)z]- and [ZnCI4l2- (all labile), and [C0(en)~]3+,
[Co(NH&I3+, [Co(en)2oxIf, [Co(en)zC03]+, c i s -
~Co(en)dN02)21+,[Co(NHds(H20)I3+, [Co(edta)]-,
[Co(N02)~l3-and [Cr(o~!~]3-(inert). Ease of preparation
and reasonable solubility ~nwater are requirements for suit-
able complex compounds.
Preparation ol trana[Co(en)2CI2b[Fe(o~)~]4% H20 (X)
.
Ks[Fe(ox)a] 3H20 is prepared by a modification of a
previous method (5).Asolution of Fe(N03)3. 9Hz0 (16.2 g i n
20 mL water, 0.04 mol) is added slowly t o a stirred hot
solution of KZOX.Hz0 (2.40 g i n 40 mL water). After cooling
in an ice hath the pale green product is filtered off, washed
with ice water, ethanol, and acetone, and air-dried.2 Yield
18.6 g, 94%.
tran.~-[Co(en)~Cl~]C1-2H~O .HC1 isobtained by oxidation
.
of a mixture of CoC12 6 H 2 0 and en with Hz02 (3.4). The
hydrate water and HCI are subsequently removed complete-
ly by heating a t 110 OC to give tran~-[Co(en)~Cl~]Cl as a
904 Journal of Chemical Education
dull green powder (16, 17). This product contains a little
cobalt(II),3and this should be removed to avoid the possible
separation of cobalt(I1) oxalate4 during the subsequent
preparation of the mixed complex. The cobalt(I1) is extract-
ed5 by stirring a suspension of trans-[C~(en)~Cl~]CI in etha-
nol. then filterine off the comalex. . . washine with acetone.
and air-drying.
Solutions are prepared of tran~-[Co(en)~Cl~]Cl (10.0 g in
40 mL of ice-cold water) and K~[Fe(ox)~] .
3H20 (4.9 g i n 35
mLof warm water, 35OC). The solutions are quickly filtered,
and the iron(II1) solution is then added to the magnetically
stirred cobalt(II1) solution. On cooling the mixture in an ice
hath the product separates as fine green crystals. These are
filtered off after 10 min,4 washed with portions of ice water
(until the filtrate is free of C1-), then with ethanol and
acetone and air-dried. Yield 6.2 g, 54%. Analysis found: C,
18.7: H. 4.9: N. 14.5: Cl. 18.4: weieht loss a t 100 'C. 6.9%.
[ C O ( C ~ H ~ N ; ) ~ C I ~ ] ~ ~ ~4112~~20
( C & ) ~requires
]'. C, 18.8; H,.
5.0;N. 14.6:Cl. 18.5:H70.7.0%.
.
t r a n s - [ ~ o ( e & ~ l ~ ] ~ [ ~ e ( 4II2H20
o x ) ~ undergoes no ap-
parent change over some days in subdued light. However,
.
like K3[Fe(ox)3] 3H20, it is photosensitive and gradually
changes to light brown with strong light, and the compound
should thus he stored in the dark.
The compound dehydrates a t 100 "C. I t rehvdrates on
standing inthe atmosphere at room temperature;apparent-
ly to the 4'2-hydrate,and thin precludes the anhydrous com-
pound being used in this project.
(1) C u d s , N. F.;Hay,R.W.; House,0. A.:Sedc, 0.H.J. Chem.Edur., 1986,63,899.
(2) Adams, 0. M.;Raynor, J. B. '"Advanced Practical Inorganic Chemistry"; Wiles
London.1966.
(15) Rc113.p63.
(16) B a i h , J. C. Inorg Synth. 1946.2.222,
(17) Springvrg. J.; Schaffer. C. E. Inorg. Synfh. 1973.14.68.
(18) Dwer, F. P. In "Aduan~esin the Chemistry of the Cwrdination Compounds":
Kirshner, S., Ed.; Maanillan: New York, 1961: p 21.
Product which is not used immediately can be recrystallized from
hot water.
Cobalt(l1)apparently arises both from me starting CoCI, and from
reduction during heating (17, 18).
'If significant cobalt(l1) is present, cobait(l1) oxalate may com-
mence to separate (as a pale pink insoluble powder) if the crystalliza-
tion of the complex is prolonged.
Cobalt(ll)can be tested for by allowinga sample of the compound
to hydrolyze in NaOH. The solution is then acidified. and KSCN is
added. The solution is shaken wim amyl alcohol to extract and
intensifyany blue Co(li)color.
 PRÁCTICA 3
Síntesis y caracterización del macrociclo de Geodken. Formación de los
complejos de Ni(II) y Cu(II).
1.1.- Preparación del complejo metálico Ni(II)-macrociclo de Geodken,
[Ni(C22H22N4)]
1.2.- Aislamiento del macrociclo de Geodken, C22H22N4.
1.3.- Preparación del complejo metálico Cu(II)-macrociclo de Geodken,
[Cu(C22H22N4)]

En esta práctica, los apartados 1.1 y 1.2 se llevarán a cabo siguiendo el

procedimiento descrito en el artículo J. Chem. Ed., 2007, 84(3), 477-479. El apartado
1.3 se llevará a cabo según el protocolo de síntesis descrito en J. Chem. Ed., 1994,
71(1), 75-77. Ambos artículos se incluyen a continuación.

Notas:

1.- Las cantidades de reactivos consideradas para la obtención del complejo [Ni(C 22H22N4)] se

modificarán con respecto a las que aparecen en el artículo. En nuestro caso utilizaremos las cantidades

de reactivos necesarias para obtener, considerando un rendimiento del 100%, 3.5 g de producto.

2.- En función de la cantidad realmente obtenida de [Ni(C22H22N4)], se conservarán

aproximadamente 150 mg de producto y el resto se utilizará como producto de partida para la obtención

del macrociclo libre.

3.- Para la obtención del complejo [Cu(C22H22N4)], las cantidades de reactivos utilizadas serán
las especificadas en el artículo correspondiente.

4.- Recristalización del reactivo 1,2-fenilendiamina. La recristalización aquí es necesaria ya que

los grupos amina se oxidan en presencia de aire a grupos nitroso que pueden reaccionar con otros
grupos amina formando grupos azo- responsables del color marrón que presenta este reactivo. El

producto rescristalizado es completamente blanco. La recristalización se lleva a cabo disolviendo el

reactivo en la mínima cantidad de EtOH, calentando para evaporar la mayoría del disolvente y enfriando
en hielo. El producto recristalizado se filtra en Büchner y se lava con un poco de éter dietílico. El

rendimiento es aproximadamente del 50%, por lo que si se necesitan 4 g de producto se utilizarán 7-8 g

de producto contaminado. Esta recristalización la pueden realizar varias parejas juntas.

 In the Laboratory

Improved Synthesis of Geodken’s Macrocycle W

through the Synthesis of the Dichloride Salt
J. H. Niewahner,* Keith A. Walters, and Ashley Wagner
Department of Chemistry, Northern Kentucky University, Highland Heights, KY 41099; *niewahnerj@nku.edu

In a continuing effort to improve our third-year inor- titative analysis was performed by Galbraith Laboratories.
ganic chemistry lab course that requires first-semester organic Spectral data are in excellent agreement (when available) to
lecture and lab, we sought the introduction of additional those published (1, 2) unless otherwise noted.
metal complexation reactions. Based on previous reports (1,
2), we chose to have the students prepare the copper and mo-
lybdenum complexes of Geodken’s macrocycle, 1, and acquire
both the emission and absorption spectra. This experiment
(and lab time restraints) required the instructor to prepare
the macrocycle in advance for the students (Scheme I). Ear-
lier reports presented the synthesis of the macrocycle in four
steps utilizing a nickel template complex, 2, with overall yields
of 40% (1) and 22% (2).
We were unsatisfied with this yield and, following some
experimentation, adapted the synthesis to eliminate one step
and increase the overall yield of 1 to 65%. This increase is
largely due to the optimization of the first step (synthesis of
2), which improved from 40% (1) to 88%. Our adapted syn-
thesis also involves the synthesis of the dihydrochloride salt
of the macrocycle, H2C22H22N4⭈2HCl, 3. Following the
preparation of 1, students can proceed with metal complex-
ation as described previously (2). This experiment provides a
more efficient method for the production of Geodken’s
macrocycle and provides an opportunity to teach students
the effect of solvent on the composition of the collected prod-
uct. In this report we present synthetic and characterization
details for the preparation of 1–3, and in the accompanying
Supplemental MaterialW we provide a complete lab handout
for students to prepare these compounds, should the instruc-
tor wish them to prepare both the macrocycle and the subse-
quent transition-metal complexes (1, 2).

Required Materials and Hazards

The following reagents are needed to complete this ex-
periment, with significant hazards also listed (3): 1,2-phe-
nylenediamine (toxic), nickel(II) acetate tetrahydrate (toxic),
acetylacetone (flammable, toxic), anhydrous n-butanol (flam-
mable, harmful), methanol (flammable, toxic), and hydro-
gen chloride gas (highly toxic). The 1,2-phenylenediamine
was obtained from Aldrich and recrystallized from ethanol
before use. The nickel(II) acetate tetrahydrate, acetylacetone,
and n-butanol were used as supplied from Aldrich. Metha-
nol (HPLC grade) was obtained from Fisher and used as sup-
plied. Hydrogen chloride gas was obtained from Linde Gas
Products.

Experimental and Results

All syntheses were carried out under normal atmospheric
conditions in a fume hood. Infrared spectra were taken with
a Nicolet Nexus 470 FT-IR using KBr pellets. NMR spectra
were acquired using a JEOL Eclipse 500 MHz NMR. Quan- Scheme I. Synthesis of Geodken’s macrocycle.

www.JCE.DivCHED.org • Vol. 84 No. 3 March 2007 • Journal of Chemical Education 477

 In the Laboratory
Preparation of NiC22H22N4 (2)
In a typical preparation for 2, 17.85 g of 1,2-phenylene-
diamine (0.1650 mole, 4 eq), 17 mL of 2,4-pentanedione
(0.17 mole, 4 eq), 10.20 g Ni(C2H3O2)2⭈4H2O (0.04100
mole, 1 eq), and 250 mL of n-butanol were added to a 500-
mL round-bottom flask equipped with a stirbar. The flask
was attached to a condenser, and the mixture was refluxed
while stirring for 3 hours using a heating mantle and mag-
netic stirrer. The mixture was then cooled to room tempera-
ture, and 50 mL of methanol was added. The solution was
then cooled to about ᎑5 ⬚C in a salt兾ice bath for about 15
minutes, during which time a dark purple–blue solid pre-
cipitated from solution. The precipitate was collected on a
Büchner funnel, washed with 30 mL of cold methanol, and
air dried, producing 14.38 g of product 2 (87.42% yield).
As previously reported (2), yields decreased with decreasing
reaction time. For each hour of decreased reaction time, we
observed a decrease of between 5–10%. However, even with
the shorter reaction times yields are better than those ini-
tially reported (40% for a three-hour reaction) (2).
IR (KBr): 1549 (arom C⫽C), 1464 (arom C⫽C), 1397
(arom CN), 1271 (arom CN), 1040 (o-disubs arom CH),
744 (o-disubs arom CH) cm᎑1.
1H
NMR (500 MHz, C6D6, δ): 1.75 (s, 12H, methyl),
4.67 (s, 2H, ⫽CH), 6.53 (m, 8H, arom).
UV–vis (CHCl3), λ nm: 285 (33,931 M᎑1cm᎑1), 394
(39,291 M᎑1cm᎑1), 428 (sh, 12,499 M᎑1cm᎑1), 588 (6,766
M᎑1cm᎑1).
While the absorption data are comparable to one previous
report (2), the absorptivities are higher than those in another
report (1). This disparity may be due to vacuum sublima-
tion of 2 conducted in the earlier report (1), which may have
removed high absorbing impurities that are possibly present
in our samples.
Preparation of H2C22H22N4⭈2HCl (3)
A mixture of 5.004 g of 2 (0.01247 moles) in 100 mL
of methanol was added to a 250-mL Erlenmeyer flask. A
stream of HCl gas was bubbled into the reaction mixture us-
ing a Pasteur pipet attached to a hose from the HCl cylinder.
The mixture changed color from green–blue to green then
brown, and the flask was very hot. The gas was bubbled
through the solution for about 20 minutes until the solution
began to drop in temperature and some white precipitate be-
gan to form. The mixture was then cooled in a 3 ⬚C ice bath
for 15 minutes, during which time more white precipitate
formed. The precipitate was collected on a Büchner funnel,
washed with cold methanol, and air dried. A yield of 4.797 g
of 3 was obtained (92.13% yield). Duplicate gravimetric analy-
sis of chloride in 3 by precipitation of silver chloride resulted
in mole ratios of HCl:macrocycle of 2.041 and 1.987.
IR (KBr): 3430 (2⬚ arom NH), 3140 (CH), 2927 (CH3),
2817 (CH3), 1570 (arom C⫽C), 1311 (arom CN), 1046
(o-disubs arom CH), 762 (o-disubs arom CH) cm᎑1.
478 Journal of Chemical Education • Vol. 84 No. 3 March 2007
1H NMR (500 MHz, D2O, δ): 2.54 (s, 12H, methyl),
4.68 (s, 2H, ⫽CH), 7.32 (m, 8H, arom).1
Quantitative Analysis, Calcd for H2C22H22N4·2HCl:
16.99 Cl, 63.30 C, 6.29 H, 13.43 N; found 18.14 Cl,
63.45 C, 6.34 H, 13.35 N. All values are given as per-
centages.
Preparation of H2C22H22N4 (1)
In a 50-mL beaker, 2.046 g of 3 (0.004902 moles) was
added along with enough methanol (5–10 mL) to form a
slurry. Triethylamine was added dropwise with stirring until
a the mixture had a pH of 9, during which time a bright
yellow precipitate formed. The precipitate was then collected
on a Büchner funnel, washed with cold methanol, and air
dried to yield 1.349 g (79.89% yield).
IR (KBr): 3450 (br) (2⬚ arom NH), 1616 (arom C⫽C),
1555 (arom C⫽C), 1363 (arom CN), 1183 (arom CN),
1040 (o-disubs arom CH), 741 (o-disubs arom CH) cm᎑1.
1H NMR (500 MHz, CDCl3, δ): 2.13 (s, 12H, methyl),
4.87 (s, 2H, ⫽CH), 6.99 (s, 8H, arom), 12.6 (s, 2H,
NH).
UV–vis (CHCl3) λ nm: 284 (22,263 M᎑1cm᎑1), 346
(37,489 M᎑1cm᎑1).
Again, these absorptivity values are higher than those previ-
ously reported (1), presumably for the same reason described
previously.
Discussion of Results
In the synthesis of 2, previous reports (1, 2) use a (2:2:1)
stoichiometric ratio of 1,2-diaminobenzene, 2,4-
pentanedione, and nickel(II) acetate tetrahydrate. However,
if the ratio is adjusted to (4:4:1) as in the current report, the
yield greatly improves. This increased yield can easily be ex-
plained on the basis of Le Châtlier’s principle. Increasing the
molar ratio of reactants as described above clearly forces the
equilibrium to the product side of the reaction, thereby in-
creasing the yield.
A more interesting result was the unexpected solvent ef-
fect upon the addition of HCl to product 2. Previously re-
ported methods (2) to produce 1 first converted nickel
complex 2 to a tetrachloronickelate(II) salt
([H4C22H22N4][NiCl4]) by using ethanol as the solvent. Fol-
lowing this precipitation, the tetrachloronickelate salt is con-
verted to the hexafluorophosphate salt of the free macrocycle
([H4C22H22N4][PF6]2). This protocol was necessary to pre-
vent nickel(II) reinsertion. However, if methanol is used in-
stead of ethanol, a solution of the dihydrochloride salt
(H2C22H22N4⭈2HCl) is instead formed. This salt eventually
precipitates when a large quantity is produced or the solu-
tion begins to cool. Interestingly, the reinsertion problem
mentioned above is not encountered here. It is likely that the
more polar methanol solvates [NiCl4]2− along with H+, leav-
ing the free macrocycle available for incorporation of the
HCl(g). Conversely, in the less polar ethanol solvent as soon
• www.JCE.DivCHED.org

as the [NiCl4]2− is formed association with [H4C22H22N4]2+
occurs and [H4C22H22N4][NiCl4] salt precipitates.
The final isolation of free macrocycle 1 proceeds as pre-
viously reported (2) with a considerably higher yield. At this
point, our students have a macrocycle that can be complexed
with various transition metals, including copper, molybde-
num, and tungsten (2, 4).
Conclusion
In this article, previously reported syntheses for
Geodken’s macrocycle were refined to produce a higher prod-
uct yield with fewer steps. Furthermore, the synthesis gives
instructors the opportunity to discuss how a slight change in
the polarity of a solvent can have quite a radical change on
the resulting product. This experiment has become one of
the most popular in our lab, with opportunities for students
to explore coordination chemistry and study the products us-
ing several spectroscopic techniques.
www.JCE.DivCHED.org • Vol. 84 No. 3 March 2007
In the Laboratory
W
Supplemental Material
Instructions for the students and notes for the instruc-
tor are available in this issue of JCE Online.
Notes
1. The amine hydrogens are presumably in rapid exchange
with the acid protons and, therefore, do not appear.
Literature Cited
1. Goedken, V. L.; Weiss, M. C.; Place, D.; Dabrowiak, J. Inorg.
Synth. 1980, 20, 115–119.
2. Chipperfield, John R.; Woodward, Simon. J. Chem. Educ.
1994, 71, 75–77.
3. Sigma–Aldrich MSDS Database. http://www.sigmaaldrich.com/
catalog/search/AdvancedSearchPage (accessed Nov 2006).
4. Cotton, F. Albert; Czuchajowska, Joanna. Polyhedron 1990,
9, 1217–1220.
• Journal of Chemical Education 479
Reliable and Economical Preparation
of Macrocyclic Complexes
Synthesis and Reactivity of a Tetraazaligand
for an Advanced Inorganic Laboratory
John R. Chipperfield and Simon Woodward
School of Chemistry, University of Hull, Cottingham Road, Hull HU6 7RX, UK
Spontaneous self-assembly reactions hold a fascination
for chemists a s we attempt to mimic anabolic reactions
without enzymes ( I ) , and synthesize new tailored poly-
mers with special electrical properties
. . (2). The ability of
certain transition metals, especially nickel, to coerce intra-
nlolecular Sch~lrs-basereactions into mncmcvcle forma-
tion is well known ( 3 , 4 ) .Undergraduates seldom have the
chance to carry out experimental work in this important
area of inorganic chemistry because published procedures
can give low yields of products with poor solubilites (51,in-
aNH2
Nitemplate No template
INHz 7
(i) HCI
(ii) 2NHaPF6
(iii) NEt3
/
Synthesis and reactions of Geodken's macrocycle.
volve difficult product separations, long reaction times (61,
or require the use of hazardous perchlorate counteranions
(7). We sought a preparation to overcome these difficulties
and yield a variety of macrocyclic complexes.
and
Of the many "macrocycle template" reactions available,
the preparation of Geodken's macrocycle 1' (the figure) is
particularly attractive (61, for the low-cost of the starting
materials, and the good solubilitylcrystallinity of most of
its complexes. The original inorganic Synthesis prepa-
ration (6) calls for a 48-hour MeOH reflux for the initial
nickel-templating reaction, well beyond the time-span
of most undergraduate laboratory classes. We found
that changing the reaction solvent to n-BuOH reduces
the reaction time to only three hours. Even shorter re-
action times are possible, but they give somewhat lower
yields of a n inferior-quality product. Use of n-BuOH re-
duces reaction time because its higher boiling point of
(118 "C) compared to MeOH (65 "C) causes both a faster
rate and preferential evaporation of water from the re-
action medium. Initially all the reactants do not dis-
solve so stirring the reaction mixture gives the best re-
sults. Comparable vields are obtained with simple
refluxing using a heiting mantle and occasional man-
ual shaking.' Stirred reaction mixtures have the advan-
a
tage that number of color changes are detected-the
initial pale green color of the [Nilo-(H2N)C6H4I3l2+ com-
plex, the formation of the purple-coloured organic 2,
and the final dark green macrocyclic complex 3 are
readily seen.
Spectroscopic data are obtained readily on the com-
plex 3 and easily assimed by students. I n particular a
clear molecular ion with the u~rrectisotope pattern at
40U mass units is observcd in thc El mass spectrum. As
the nickel complex is diamagnetic, the r&ulting 'H
NMR spectrum affords good teaching opportunities to
demonstrate the reduction in the number of signals pre-
sented by a high symmetry species.
The macrocyclic complex is stripped easily of i t s
nickel template by the published procedure (6). Addi-
tion of HC1 gas results in turquoise [Hylacl[NiClJ, and
then the nickelate anion is replaced by two PFs moie-
ties.3 The presence of a base yields the yellow free
'Because the full name of this compound, S,l4-dihydro-
6,8,15,17-tetramethyldibenzo[b.il-[l,4,8,111 tetraazacyciotetra-
decahexene, is torturously long, we call it 'the macrocycle' here
and write it as (H,Mac).
2Some slight contamination with unreacted 1.2-di-
arninobenzene often is encountered , but this is removed when
the free macrocycle is isolated.
3The ditetrafluoroboratesalt is water-soluble so no economies
may be effectedhere by use of NaBF,.
Volume 71 Number 1 January 1994 75
macrocycle [HzMacl 1,with nickel contamination directly
orooortional to the ereenness of the samole. Because
~ H ~ M ~is C quite
] ~ reactive
+ it is best to these spe-
cies and final macrowcle in one laboratory session. The
isolated macrocycle gives excellent spectr~scopicresults
for most techniques, offering many possible teaching exer-
cises.
The ready supply of 1 allows a range of complexation
studies to be undertaken in the laboratory. Reaction of 1
with C U ( O ~ C M ~ ) ~ allows
. H ~ O easy preparation of the cop-
per complex CuIMacl, 4, isostructural with the nickel com-
plex (8).More interestingly, the thermal reaction of 1with
MO(CO)~ yields the unusual species 5, the product of a hy-
drogen mieration reaction (9). The oresence of a remaining
~ ~ ~ f u n c t is
r odetected
n i n t h e IR spectrum, VNH (KBrj
3420 ern-'. and bv 'H NMR soectroscoov where a high fre-
quency amine is observed, ~"'(cDc~) 12.54. The
lower svmmetrv of the comolex 5 is also aovarent by the
greatei number of signals bbserved in t h e proton spec-
trum, Srr (270 MHz. CDCl4 1.93 (s. 6 H. Me), 2.05 (s. 6 H,
Me), 3.87 (apparent s, 2 H, CH,), 4.53 (s, 1H, CHI, 6.93-
7.20 (m, 8 H, aromatics), and 12.54 (s, 1H, NH). In amee-
ment with its C, symmetry, four carbonyl stretches a& ob-
served by vibrational spectroscopy, vco (KBr) 2005, 1897,
1875, and 1835 em-'. A tungsten analogue of 5, prepared
similarly, is structurally characterized (10).
Experimental
All reagents were used a s supplied except 1,2-
diaminobenzene (phenylenediamine) that was purified by
a single recrystallization from EtOH in the presence of de-
colorizing charcoal. The solvents "BuOH and EkO were
dried over 4Amolecular sieves. Preparation times and iso-
lated yields represent typical student values. Experienced
workers will complete the experiments in less time and
higher yield.
Preparation of the Nickel Macroc clic Complex
(4-6 h depending on experience{
A 100-mL short-necked round-bottomed flask was
charged with a spinbar, Ni(OzCMe)z.4Hz0(2.00 g, 8.03
mmol), 1,2-diaminobenzene (phenylenediamine) (1.73 g,
16.01 mmol), dry butan-1-01 (30 mL), and acetylacetone
(2.4-oentanedione)(1.7 mL. -16.6 mmol) added bv svrinae.
The flask was set up in an oil bath on a hot pl&esti<er
(alternatively a heating mantle may be used instead, but a
few boiling chips must be added) &d equipped with a re-
flux condenser. The mixture was brought to a brisk reflux
and stirred under reflux (3h),noting any color changes. (If
a heating mantle was used, the reaction mixture was
gently swirled occasionally
Thick nonmelting gloves were used to avoid bums.
This was esoeciallv imoortant in the initial stage of the
reaction befire a l l i f the reagents were in solutyon.) The
flask was removed from the heat source and allowed to cool
until just warm to touch (- 30 C).Methanol (30 mL) was
added and the mixture was cooled in an ice-salt bath for a t
least 15 min to precipitate the nonpolar macrocyclic com-
plex. When filtered onto a 20-mm glass frit and washed
with MeOH (about 2 x 10 mL; the washings should be col-
orless to pale green) afforded dark purple microcrystals
1.20-1.30 g (3740%).A 100-mgsample of product was re-
tained. The rest of the product was converted to free
macrocycle as outlined below.
-
40vernightcooling at 4 OC gives much higher yields (about65%).
76 Journal of Chemical Education
Preparation of/H~(Macrocycle)]/NICl~]
(up to 1 h depending on experience)
The nickel complex (1.10 g, 2.81 mmol) was suspended in
absolute EtOH (30 mL) in a 100-mL round-bottomed flask
-~
in a fume hood. A moderate stream of HCI eas (from ,--~~-~a
~
ledure-bottle fitted with a rubber tube and ~ a s t e upipet,
r
-~
- 10 bubbles s-'1 was bubbled through the suspension, ag-
itating occasionally.
Caution: The mixture gets quite warm.
Once a copious quantity of turquoise precipitate had
formed it was filtered off and washed with absolute EtOH
(10 mL) and EtzO (2 x 10 mL) giving 1.43 g (95%)of prod-
uct.
Isolation of the Free Macrocycle
(about I h depending on experience)
The turquoise tHdMac)l[NiClJ salt (1.43 g, 2.66 mmol)
was dissolved in water (10 mL). Occasionally white, water
insoluble, impurities were present at this stage and these
were removed by filtration. (It was most convenient to use
the glass frit onto which the [H4(Mac)l[NiC141 was isolated
onto in the previous preparation.) The frit was rinsed
through with further water (5 mL). Solid [NH41[PFs1(1.00
g, 6.13 mmol) was added to the filtrate and swirled until a
large amount of white ~ r e c i o i t a t eformed. The
[H~TM~C)I[P was
F ~filtered
I~ iff on;o a clean 20-mm glass
frit and washed with cooious amounts of water (- 20 mL)
until the product was pale green. (In this step the
[NH~ldNiCl~l by-~roductneeds to be washed awav ore-
venting nickel from re-inserting into the macrocyle b'ba-
sification; use of too much water resulted in ~roductloss.)
The sticky product was transferred to a 5 b - m ~conical
flask washing any spatulas and the frit off with MeOH into
the conical flask to maximize the mass of [H4(Mac)I[PF61Z
transferred. Enough MeOH should be present in the flask
to cover the salt. In a fume hood Et3N was added drop-
wise to the suspension and swirled until pH 9 was at-
tained. The free yellow macrocycle was filtered off onto a
clean frit, washed with MeOH, and air dried yielding 0.54
g (59%).
Reaction of C u ( Q C M e h M 0 with the Macrocycle
(1-2 h depending on experience)
A 100-mL conical flask was charged with
C U ( O ~ C M ~ ) ~ .(0.12
H ~ O g, 0.60 mmol), a spinbar, and
MeCN (40 mL), fume hood. The flask was equipped with
a condenser and refluxed until all of the C U ( O ~ C M ~ ) ~ . H ~ O
had dissolved. A suspension of the macrocycle (0.20 g, 0.56
mmol) in MeCN (10 mL) containing NEt3 (0.2 mL), fume
hood, was added down the reflux condenser and residual
macrocycle washed in with a extra 1-2 mL of MeCN. The
resulting dark-ereen solution was refluxed (10 mid. al-
lowed tocool totoroomtemperature, cooled in ice (20 ;din).
After filtering off, the dark green microcrystalline product
was washed with MeCN (2 x 2 mL), EkO (2 x 2 mL) and air
dried, yielding 0.16 g (35%)?
Reaction of Mo(C0)G with the Macrocycle
(3-4 h depending on experience)
The macrocycle (0.25 g, 0.73 mmol) and Mo(CO)G(0.19 g,
0.72 mmol) were placed in a 50-mL round-bottomed flask
together with a spinbar, and toluene (15 mL). The flask
was equipped to allow refluxing under a inert atmosphere,
brought slowly to the boil and then refluxed (1h), noting
all changes. The reaction flask was allowed to cool to room
temperature under nitrogen. The stoppered flask was
cooled in an ice bath (30 min) and then the mother liquors
were pipeted off. The crude reaction product was purified
by recrystallization. The yellow-brown solid was dissolved
in the minimum amount of CHzC12(-20 mL), and filtered
into a 50-mL conical flask. The reaction residue was ex-
tracted with a further 1-2 mL of CH& and this fdtered
into the conical flask as well. Light petroleum (hp 40-60
"C) was added to the to the filtrate, with a n occasional
slight swirl, until it became very turbid, slightly cloudy, or
started to crystallize (a volume approximately equal to
that of the CH2Clz added was normally required). The
stoppered flask was woled to 0 OC (1 h) during which time
yellow crystals appeared. The mother liquor was pipeted
away and the crystals washed with a few milliliters of light
petroleum. The residual petroleum was evaporated to
yield bright-yellow crystals 0.12 g (30%).
Literature Cited
1. Ghadul, M. R.;Soares,C.; Choi, C. J Am. Cham. Soe. 1992,114,825-831.
2. Marhs, T J.Ang~uiCham., Inr. Ed En&. 1990.29.857-879.
3. Lindoy L. F The Chemistry ofMmmcyclic Lrgond comple%zs: Cambridge u n i v e r
sity Press:Cambridge, 1989.
4. sacmni, L.; Mani, F: Benci"i,A. lnComp4he"si"e Coordi~fio"chemistry; Wilkin-
son, G.; Gillsrd, R. D.; McCleverty, J. A . Eds; Pergapaman Press:Oxford. 1981; Vol.
5, Chapter 5, Sed.505.9.
5. Merrell, P H.: Urhaeh, F h h d d , M.J Cham. Educ. 1977,M,580-582.
6. Goedken. V . L.: Weisa, M.C.: Place, D.: Dabmwiak. J. Inorg. S W h . 1980. 20. 11&
119.
7. Tait, A. M.; Buseh. D. H.; Curtis, N. F. Inorg Synfh. 1978,18,2-9.
8. W m d d ,W. H.: Pastor, R. W.: Dabmeak, J. C. J. Am. Chem. Sac. 1916,98.799%
8W6.
9. Bell, L. G.:Oabmwiak, J. C. J Chem. Sor Chem. Commun. 1975,512-513.
10. canon, F A ; czuchajowska,~.~ o t y h d m nISSO.9. 1217-1220.
Volume 71 Number 1 January 1994 77
 PRÁCTICA 4
Síntesis y caracterización de un complejo termocrómico de transición de
espín de Fe(II).

1.1.- Preparación de una disolución acuosa de bromuro de hierro(II), FeBr2.

1.2.- Síntesis del complejo metálico [Fe(NH2Trz)3]Br2·H2O.

1.3.- Caracterización del complejo y estudio de sus propiedades ópticas,

magnéticas y espectroscópicas.
1.1.- Preparación de una disolución acuosa de bromuro de hierro(II),
FeBr2.
4 mmol de sulfato de ferroso heptahidratado se disuelven en 50 mL de agua
destilada y la disolución resultante se calienta suavemente a 80 ºC. Sobre ésta, se
añaden gota a gota y bajo agitación, 10 mL de una disolución acuosa de bromuro de
bario(II) dihidratado (6 mmol). Igualmente se añaden aproximadamente 10 mg de ácido
ascórbico.

Completada la adición la mezcla de reacción se mantiene a 80ºC, sin agitación

durante 90 min. añadiendo agua destilada si es necesario a fin de mantener un volumen
cercano a 30 mL (aproximadamente). Pasado este tiempo, la mezcla de reacción se
enfría en un baño de hielo y se filtra cuidadosamente en Büchner. El precipitado de
BaSO4 se lava dos veces con 10 mL de agua destilada.

1.2.- Síntesis del complejo metálico [Fe(NH2Trz)3]Br2·H2O.

La disolución de FeBr2 obtenida en el paso previo se vierte sobre un vaso de
precipitado de 250 mL, se agita y sobre la misma se pasa una corriente de N2(g) durante
aprox. 2 min. A continuación se añaden, poco a poco y manteniendo la agitación, 12
mmol del ligando 4-amino-1,2,4-Triazol. La mezcla resultante se mantiene bajo una
corriente de N2(g) durante aproximadamente 5 min.

La mezcla se enfría en un baño de hielo y se filtra sobre Büchner. El precipitado

obtenido se lava con 10 mL de agua fría desgasificada (previamente se le ha pasado una
corriente de N2(g)).

Finalmente, el precipitado obtenido se seca sobre papel de filtro.

1.2.- Caracterización del complejo [Fe(NH2Trz)3]Br2·H2O: propiedades
ópticas, magnéticas y espectroscópicas.
1.2.1.- Propiedades ópticas: Termocromismo y biestabilidad.

En dos tubos de ensayo, colocar aproximadamente 500 mg del complejo

obtenido:

- Introducir uno de los tubos en una mezcla de hielo/sal. Anotar los cambios
observados.

- Introducir el otro tubo en agua caliente (en torno a 80 ºC). Anotar los cambios
observados.

- Introducir ambos tubos en agua a temperatura ambiente. Observar los cambios

producidos.

1.2.2.- Propiedades magnéticas.

Colocar el tubo de ensayo que contiene el complejo de color blanco sobre unas
pinzas y aproximar, sin llegar a tocar el tubo de ensayo, un imán permanente de NdFeB.
Observar qué sucede.

A continuación, colocar el tubo de ensayo en agua fría hasta que el producto

adopte un color violeta. Repetir el procedimiento anterior.

1.2.3.- Caracterización espectroscópica.

1.2.3.1.- Espectroscopía infrarroja.

Medir los espectros IR del complejo [Fe(NH2Trz)3]Br2·H2O y del ligando

NH2Trz. Comentar los resultados obtenidos.

1.2.3.1.- Espectroscopía Visible.

Se han llevado a cabo medidas de reflectancia difusa sobre el complejo obtenido

entre 800 y 400 nm. Un primer espectro se ha tomado para la muestra con el color
violeta. Esta misma muestra se ha calentado hasta inducir la transición termocrómica y a
continuación se ha medido un nuevo espectro. Comentar las diferencias con la ayuda de
un diagrama de Tanabe-Sugano para una configuración electrónica 3d6.
Señal Reflectancia Difusa / a.u.

Señal Reflectancia difusa / u.a.

T = 400 K

1 1
1 1 A1g T1g
A1g T2g

350 400 450 500 550 600 650

/ nm

T = 280 K

T = 400 K

300 400 500 600 700 800

/ nm
 Laboratory Experiment

pubs.acs.org/jchemeduc

Synthesis and Properties of a Thermochromic Spin Crossover FeII

Complex: An Undergraduate Coordination Chemistry Laboratory
Experiment
Anne Vallée,† Cyrille Train,‡,∥ and Cécile Roux*,†
†
Laboratoire de Chimie de la Matière Condensée de Paris, UMR CNRS 7574, UPMC Univ Paris 06, Collège de France, 11 place
Marcelin Berthelot, F-75231 Paris Cedex 05, France
‡
Laboratoire National des Champs Magnétiques Intenses, UPR CNRS 3228, Université Joseph Fourier, F-38042 Grenoble, France
∥
Institut Universitaire de France (IUF), 103, bd Saint-Michel, F-75005 Paris, France
*
S Supporting Information

ABSTRACT: In this third-year undergraduate experiment, a coordination

complex [Fe(NH2trz)3]Br2·H2O (NH2trz is 4-amino-1,2,4-triazole, C2H4N4) was
synthesized and characterized by IR and UV−visible spectroscopies. This
compound exhibits a spectacular reversible purple-white thermochromic transition
upon heating−cooling with a large hysteresis centered at room temperature. The
thermochromic transition is related to the spin crossover (SCO) from the low-spin
state (LS, purple, S = 0, diamagnetic) to the high-spin state (HS, white, S = 2,
paramagnetic). During this experiment, students discovered synthetic methods,
such as anion metathesis and Ostwald ripening, and physical properties, such as
magnetic properties, thermochromism, and bistability phenomenon, altogether
leading to possible applications in optical-data storage and display.

KEYWORDS: Upper-Division Undergraduate, Inorganic Chemistry, Laboratory Instructions, Hands-On Learning/Manipulative,

Coordination Compounds, Crystal Field/Ligand Field Theory, IR Spectroscopy, UV-Vis Spectroscopy

A n important goal in modern chemical education is to

provide students with experiments that reinforce
fundamental concepts learned in the classroom and simulta-
neously address potential applications. In laboratory experi-
ments of coordination chemistry, undergraduate students
synthesize complexes and characterize their properties using
the general concepts of synthesis, vibrational and electronic
spectroscopies, and ligand field theory.1−11 The objectives are
generally to study electronic configurations, optical properties,
and magnetic properties as a function of metal identity,2,4,8,9
ligand field strength, 2,8,9 and geometry of the com-
plexes.1,3,5,7,10,11 However, the potential applications are
scarcely discussed. It is worth noticing that introducing
considerations related to applied science in an inorganic
experimental work requires supplementary knowledge, for
instance, in reactivity, kinetics, and materials science. General
concepts are then prerequisites rather than reinforced notions.
Spin crossover (SCO) complexes are essentially d4−d7 first-
row transition-metal octahedral complexes whose potential
applications can be basically understood using the general
concepts listed above. These complexes undergo a reversible
spin change from high spin (HS) to low spin (LS) as a function
of external stimuli, such as temperature, pressure, or light.12
The spin-state change is associated with modifications of
magnetic properties and often with thermochromic properties.
If there are sufficient interactions between the SCO units, the
© 2013 American Chemical Society and
Division of Chemical Education, Inc.
SCO can also present a thermal hysteresis leading to bistable
systems, making these materials of large interest for use in data-
storage devices.13 To our knowledge, only one previous
experiment has been reported concerning the study of SCO
complexes that focused on magnetic measurement.6 Other
experiments deal with thermochromic compounds;1,3,10,11
however, they do not use SCO compounds and do not discuss
corresponding applications.
[Fe(NH2trz)3]Br2·H2O (NH2trz is 4-amino-1,2,4-triazole;
Figure 1A) was selected because of its ease of synthesis and its
reversible thermochromic SCO transition with a thermal
hysteresis centered at room temperature (RT). These
conditions are ideally suited (i) to illustrate the general
concepts of an advanced undergraduate inorganic chemistry
course and (ii) to set up this experiment in an inorganic
chemistry laboratory with RT characterizations by usually
available techniques. Following the structure published with the
nitrate as a counterion, the compound should consist of linear
chains where the Fe(II) ions are triply bridged by the N(1)−
N(2) atoms of the triazole ligands (Figures 1B and 1C).14
A new, easy, and inexpensive synthesis of the complex
[Fe(NH2trz)3]Br2·H2O was developed that was based on
Lavrenova et al. synthesis of similar complexes [Fe(NH2trz)3]-
Published: June 18, 2013
1071 dx.doi.org/10.1021/ed4000487 | J. Chem. Educ. 2013, 90, 1071−1076
Journal of Chemical Education
Figure 1. (A) Structure of 4-amino-1,2,4-triazole, NH2trz. (B)
Detailed and (C) schematic structures for [Fe(NH2trz)3]Br2·H2O,
adapted from ref 14.
X2·H2O (X = I−, NCS−, Cl−).15,16 As the thermally induced
SCO properties (hysteresis position and width) are sensitive to
synthetic conditions, solvents, anions, and ligands,15,16
magnetic measurements were performed by the authors on
this compound. The thermal variations of the χM·T product,
where χM is the molar paramagnetic susceptibility corrected
from diamagnetic contributions17 and T, the temperature, are
shown in Figure 2 (right scale). Because the LS form is
Figure 2. Thermal variations of χM·T (filled squares) for [Fe-
(NH2trz)3]Br2·H2O, recorded by the authors at 1 K/min on a SQUID
magnetometer available in research units, and calculated γHS (solid
lines); T↑ and T↓ are the temperatures corresponding to γHS = 50% in
heating and cooling modes, respectively.
diamagnetic, the χM·T product gives a direct access to the HS
molar percentage γHS(%)18 in the sample (Figure 2; left scale).
The first-order LS ↔ HS transition occurred with a hysteresis
of 35 K centered around 297 K for a sweeping rate of 1 K/min
(Figure 2).15,16,19 These accurate magnetic measurements are
not easily accessible with usual teaching laboratory techniques.
In this experiment, two properties of an SCO complex, its
thermochromic phenomenon and its bistability at RT, are used
1072
Laboratory Experiment
to bypass this problem. The former is a means to easily follow
the SCO, whereas the latter allows both spin states to be
determined at RT for its characterization. Furthermore, these
approaches open the possibility to illustrate experimentally the
principle of optical-data storage.
The objectives of this experimental work were the following:
(a) Synthetize the [Fe(NH2trz)3]Br2·H2O complex and
characterize it by IR spectroscopy.
(b) Highlight the thermochromic effects by visual observa-
tions upon heating−cooling treatments.
(c) Evidence the bistability effects by visual observations
upon heating−cooling treatments.
(d) Observe qualitatively the magnetic properties of both
colored forms and relate the observed colors to the spin
states of the compound.
(e) Understand the principle of optical-data storage by using
electronic spectroscopy.
(f) Put into practice general concepts of ligand field theory,
electronic configurations, spectroscopic terms, and
electronic transitions to interpret the electronic spectra.
This experiment was developed for the advanced third-year
bachelor level. It has been performed every year since 2005
with groups of 12 students (at most) working in pairs.
■
EXPERIMENTAL DETAILS
The synthetic details, typical results acquired by students, and
supplementary data are provided in the Supporting Informa-
tion. The entire experiment requires two 3-h lab periods, the
first being devoted to synthesis and the second to product
collection and characterization. This experiment can be
condensed into one 4-h period beginning at the second step
of the synthesis or characterizing the products previously
synthesized by other students. The latter procedure was chosen
so that the students can understand the relationship between
the color and the spin state prior to seeing the numerous color
changes during the second step of the synthesis. Students
record all observations and write the answers to the questions
(available in the Supporting Information) in their laboratory
book.
■ SYNTHESIS OF [Fe(NH2trz)3]Br2·H2O
The main features of the synthesis are given below. Metathesis
and Ostwald ripening are the important points to discuss with
students. In the first step, an aqueous solution of iron(II)
bromide was obtained starting from iron(II) sulfate, a common
iron(II) salt (Figure 3), by performing an anion metathesis
according to the following reaction:
Fe2 +(aq) + SO4 2 −(aq) + Ba 2 +(aq) + 2Br −(aq)
⇌ BaSO4 (s) + Fe2 +(aq) + 2Br −(aq)
Barium(II) sulfate precipitated as a very thin powder. It was
thus necessary to perform an Ostwald ripening prior to
filtration (Figure 3).
In the second step, 4-amino-1,2,4-triazole was added to the
iron(II) bromide filtrate. The complex was obtained by
evaporation of the solution containing the iron(II) bromide
filtrate and 4-amino-1,2,4-triazole using nitrogen gas flow
(Figure 4):
dx.doi.org/10.1021/ed4000487 | J. Chem. Educ. 2013, 90, 1071−1076
Journal of Chemical Education
Figure 3. Preparation of an aqueous solution of iron(II) bromide.
Figure 4. Synthesis of the complex [Fe(NH2trz)3]Br2·H2O.
Fe2 +(aq) + 2Br−(aq) + 3NH 2trz(aq) + H 2O
⇌ [Fe(NH 2trz)3 ]Br2·H 2O(s)
■
CHARACTERIZATION
The IR spectra of the [Fe(NH2trz)3]Br2·H2O complex and of
the NH2trz ligand in KBr pellets (2%) were recorded between
550 and 4000 cm−1. The thermochromism and bistability
phenomena were qualitatively observed by warming or cooling
500 mg of the solid complex in a test tube. The magnetic
properties were qualitatively observed by bringing an NdFeB
permanent magnet close to the complex in a test tube
suspended to a retort stand. The electronic spectra were
recorded between 800 and 400 nm in the solid state (KBr pellet
10%) at RT after different thermal treatments.
■
HAZARDS
Iron(II) sulfate heptahydrate is harmful if swallowed and can
cause serious eye irritation and skin irritation. Barium(II) salts
are harmful if inhaled or swallowed. 4-Amino-1,2,4-triazole,
potassium bromide, and iron(II) bromide are irritating to the
eyes, respiratory system, and skin. Iron(II) bromide is also
harmful if inhaled. The safety instructions are included in the
Instructors’ Notes in Supporting Information. In line with the
precautionary principle, it is appropriate to lay down added
safety requirements to cover the unknown potential hazard
presented by the synthesized complex [Fe(NH2trz)3]Br2·H2O.
1073
Laboratory Experiment
■ RESULTS AND DISCUSSION
Synthesis
A small minority of the students, 5%, failed to obtain the
desired SCO product because they used the solid BaSO4
instead of the FeBr2 filtrate. The other students were able to
obtain the product without complication with a yield ranging
between 46% and 60%. However, the SCO properties were
more spectacular if the conditions described in the
experimental protocol were strictly followed.20
IR Characterization
The IR spectra showed typical features for aromatic cyclic
amines and their coordination complexes: the stretching
vibrations bands of the triazole cycles were found in the
1350−1600 cm−1 range and were shifted to higher wave-
numbers with a broadening of the peaks upon coordination to
iron(II).21 In parallel, the presence of two bands at 620 and 680
cm−1 on both spectra indicated the same C2v symmetry for
NH2trz in its free and coordinated forms, suggesting that two
iron(II) ions are linked by N(1)−N(2) triazole bridges.22 No
effect of the SCO is observed in the 4000−550 cm−1 region:
the white- and purple-colored solids exhibited the same IR
spectra.
Thermochromism
The thermochromism was visually observed during the
synthesis. At the end of the evaporation, a white powder was
observed. The powder became (slightly) purple when placed in
dx.doi.org/10.1021/ed4000487 | J. Chem. Educ. 2013, 90, 1071−1076
Journal of Chemical Education Laboratory Experiment

an ice bath and remained purple when brought back to RT

(Figure 4).23 Students concluded that the purple complex was
favored at low temperatures, whereas the white complex was
favored at high temperatures.
Bistability
The color change depended on the thermal history of the
compound, that is, its bistability. Treatment at 273 K was not
sufficient to convert the entire sample to a single color. Use of
liquid nitrogen or a warm water bath (340−350 K) was
necessary to achieve full conversion of the complex either to a
purple color or to a white color, respectively. Typical
observations of students are shown in Figure 5. Both colors

Figure 5. Photographs at RT of student results showing tube

containing the sample [Fe(NH2trz)3]Br2·H2O suspended to a retort
stand (A) after cooling at 77 K and (B) after heating at 353 K. The
white form (B) is attracted to the magnet, whereas the purple form
(A) is slightly repelled by the magnet.

were stable at RT and observable even after numerous thermal

treatments. Students thus demonstrated the hysteretic charac-
ter, the reversibility, and the cyclability of the thermochromic
transition.
Magnetic Properties
The formation of both states at RT made possible a qualitative
magnetic characterization: students observed that the purple
form was weakly repelled by a permanent magnet (Figure 5A),
whereas the white form was attracted to a permanent magnet
(Figure 5B).23 The purple form was then a diamagnetic
compound having all of its electrons paired. A ligand field
approach states that the iron(II) center is in its t2g6 low-spin
state. On the contrary, a paramagnetic behavior was observed
for the white form due to presence of four unpaired electrons in
the t2g4eg2 high-spin state.
Optical-Data Storage
To quantify the optical response of the system, electronic
spectra were recorded by students at RT after various thermal
treatments (Figure 6). A RT typical spectrum of the iron(II)
compound in a KBr pellet presented an absorption band with a
rounded maximum at λmax = 530 nm (medium green). Because
there was only one absorption band in the visible range,
students quickly concluded that this band was at the origin of
the observation of the purple complementary color. When the
pellet was heated, the absorption at 530 nm decreased,
indicating a decrease amount of the purple form.24 However,
the absorption at 530 nm increased after the pellet was
1074
Figure 6. (Top) Student’s electronic spectra of [Fe(NH2trz)3]-
Br2·H2O in KBr pellet recorded at RT after different thermal
treatments. (Bottom) Simplified Tanabe−Sugano diagram for d6
octahedral complexes (E, energy of excited terms taking the energy
of ground state equal to zero; B, Racah parameter; Δ, ligand field; P,
electron pairing energy).
immersed in liquid nitrogen due to an increased amount of the
purple form. Students thus understood that measuring the
optical density at λ = 530 nm was a way to read the information
stored in the material after an appropriate thermal treatment to
encode the information.
Interpretation of the Electronic Spectra
The purple color was stronger for the sample immersed in
liquid nitrogen, though not very intense. A d−d transition was
suggested by students for the band centered at λmax = 530 nm
and a d6 Tanabe−Sugano diagram used for its interpretation.25
Assuming B/B0 = 0.75 and B0 = 1058 cm−1, the only possible
transition was the first spin-allowed transition in the high-field
region (right part), that is, 1A1g → 1T1g.
Students obtained a value for the ligand field for the LS state,
Δo(LS), of ca. 20 790 cm−1. This value was slightly higher than
the typical pairing energy in iron(II) octahedral complexes (15
000 cm−1). It was in the range expected for compounds
exhibiting thermal SCO properties (Table 1). The values given
in Table 1 allowed evaluating the wavelength range expected
for the only spin-allowed transition 5T2g(HS) → 5Eg for the HS
dx.doi.org/10.1021/ed4000487 | J. Chem. Educ. 2013, 90, 1071−1076
Journal of Chemical Education
Table 1. Values of the Ligand Field Expected for a
Octahedral Fe(II) Compounds
Compound Δo(HS)/cm−1a Δo(LS)/cm−1a
HS <11000 
SCO ≈ 11500−12500 ≈ 19000−22000
LS  >23000
a
Data from ref 25.
state: it was expected in the near-IR region.26 This explained
why no d−d band was observed in the UV−visible spectra of
the HS form.
■
CONCLUSION
This experiment was performed by 200 students. The
effectiveness of the experiment in achieving its objectives was
assessed in several ways. First, by direct observation of both
colors at RT it was possible to assess the experimental
proficiency of the students (cf. Supporting Information).
Second, the students’ ability to report experimental findings
in a scientifically acceptable format was directly assessed from
the quality of the laboratory books that must include their
experimental observations and their answers to questions given
in Supporting Information. Lastly, student and instructor
comments were collected at the end of each semester; in
general, this experiment was well received by students. The
thermochromism and the optical-data storage property was
always a great astonishment. They discovered the macroscopic
effect of para- and diamagnetism for coordination compounds.
The instructors noticed that (1) all students were able to
correlate a color to a spin state for this complex; (2) they no
longer associated the SCO phenomenon with a redox reaction;
(3) they progressed in the understanding of the general
concepts of the course such as the existence of two spin states
in octahedral iron(II) complexes, the electronic transitions, the
interpretation and use of Tanabe−Sugano diagrams, and the
magnetic properties. It is necessary to note that the spectacular
thermochromism of this complex facilitated their under-
standing.
Finally, the setup for this experiment is simple to implement.
It can be adapted to lower levels by shortening the
characterization work or to the master level by adding
quantitative magnetic measurements27 or by extending the
study to other related magnetic complexes.
■
ASSOCIATED CONTENT
*
S Supporting Information
Student handouts; instructor notes, including IR and UV
spectra; CAS registry numbers of chemicals; manufacturers of
equipment; IR spectra. This material is available via the Internet
at http://pubs.acs.org.
■ AUTHOR INFORMATION
Corresponding Author
*E-mail: cecile.roux@upmc.fr.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
The authors wish to thank A. Proust, for implementing this
laboratory experiment in the program of her course, M.
1075
Laboratory Experiment
Verdaguer who has largely diffused this work in many
congresses, O. Durupthy for his implementation and helpful
participation, T. Coradin for his corrections, and the reviewers
for their constructive comments.
■
REFERENCES
(1) Bare, W. D.; Mellon, E. K. Thermochromic behavior of cobalt(II)
halides in nonaqueous solvents and on filter paper. J. Chem. Educ.
1991, 68, 779−780.
(2) Battle, G. M.; Allen, F. H.; Ferrence, G. M. Teaching three-
dimensional structural chemistry using crystal structure databases. 3.
The cambridge structural database system: information content and
access software in educational applications. J. Chem. Educ. 2011, 88,
886−890.
(3) Cui, A.-L.; Chen, X.; Sun, L.; Wei, J.-Z.; Yang, J.; Kou, H.-Z.
Preparation and thermochromic properties of copper(II)-N,N-
diethylethylenediamine complexes. J. Chem. Educ. 2011, 88, 311−312.
(4) de Berg, K. C.; Chapman, K. J. Determination of the magnetic
moments of transition metal complexes using rare earth magnets. J.
Chem. Educ. 2001, 78, 670−673.
(5) Gray, H. B. Chemical applications of group theory (Cotton, F.
Albert). J. Chem. Educ. 1964, 41, 113−114.
(6) Hutchinson, B.; Hance, R. L.; Hardegree, E. L.; Russell, S. A. A
simple demonstration of the Curie-Weiss law and a spin-crossover
compound. J. Chem. Educ. 1980, 57, 830−831.
(7) Linenberger, K.; Bretz, S. L.; Crowder, M. W.; McCarrick, R.;
Lorigan, G. A.; Tierney, D. L. What is the true color of fresh meat? A
biophysical undergraduate laboratory experiment investigating the
effects of ligand binding on myoglobin using optical, EPR, and NMR
spectroscopy. J. Chem. Educ. 2011, 88, 223−225.
(8) Pernicone, N. C.; Geri, J. B.; York, J. T. Using a combination of
experimental and computational methods to explore the impact of
metal identity and ligand field strength on the electronic structure of
metal ions. J. Chem. Educ. 2011, 88, 1323−1327.
(9) Sutton, L. E. Some recent developments in the theory of bonding
in complex compounds of the transition metals. J. Chem. Educ. 1960,
37, 498−505.
(10) Lavabre, D.; Micheau, J. C.; Levy, G. Comparison of
thermochromic equilibria of Co(II) and Ni(II) complexes. J. Chem.
Educ. 1988, 65, 274−277.
(11) Spears, L. G., Jr.; Spears, L. G. Chemical storage of solar energy
using an old color change demonstration. J. Chem. Educ. 1984, 61,
252−254.
(12) Gütlich, P.; Goodwin, H. A. Spin CrossoverAn Overall
Perspective Spin Crossover in Transition Metal Compounds I; Springer:
Berlin/Heidelberg, 2004; Vol. 233, pp 1−47.
(13) Kahn, O.; Martinez, C. J. Spin-transition polymers: from
molecular materials toward memory devices. Science 1998, 279, 44−48.
(14) Grosjean, A.; Daro, N.; Kauffmann, B.; Kaiba, A.; Letard, J.-F.;
Guionneau, P. The 1-D polymeric structure of the [Fe(NH2trz)3]-
(NO3)2·nH2O (with n = 2) spin crossover compound proven by single
crystal investigations. Chem. Commun. 2011, 47, 12382−12384.
(15) Lavrenova, L. G.; Shakirova, O. G.; Ikorskii, V. N.; Varnek, V.
A.; Sheludyakova, L. A.; Larionov, S. V. 1 A 1 ⇄ 5 T 2 spin transition in
new thermochromic iron(II) complexes with 1,2,4-triazole and 4-
amino-1,2,4-triazole. Russ. J. Coord. Chem. 2003, 29, 22−27.
(16) Lavrenova, L. G.; Yudina, N. G.; Ikorskii, V. N.; Varnek, V. A.;
Oglezneva, I. M.; Larionov, S. V. Spin-crossover and thermochromism
in complexes of iron(II) iodide and thiocyanate with 4-amino-1,2,4-
triazole. Polyhedron 1995, 14, 1333−1337.
(17) Bain, G. A.; Berry, J. F. Diamagnetic Corrections and Pascal’s
Constants. J. Chem. Educ. 2008, 85, 532−536.
(18) γHS(%) = 100 × xHS = (χM·T)exp/(χM·T)HS with xHS the molar
quantity of iron(II) ions in the HS form per iron center and (χM·T)HS
= 3.3 cm3 K mol−1 with gFe = 2.1 the value of the χM·T product when
all the iron(II) ions are the HS form.
(19) Rotaru, A.; Varret, F.; Gindulescu, A.; Linares, J.; Stancu, A.;
Létard, J. F.; Forestier, T.; Etrillard, C. Size effect in spin-crossover
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Journal of Chemical Education Laboratory Experiment

systems investigated by FORC measurements, for surfacted [Fe(NH2-

trz)3](Br)2.3H2O nanoparticles: reversible contributions and critical
size. Eur. Phys. J. B 2011, 84, 439−449.
(20) In the first step, the temperature and the time were the
important parameters to control to avoid BaSO4 impurities in the final
product. In the worst cases, a filtration (Celite) or centrifugation step
was necessary to obtain a clear filtrate. In the second step, the students
who were lacking time could finish the water evaporation using a
rotary evaporator. However, the quality of the final product increased
with the volume of water that was evaporated under N2 flow.
(21) Sinditskii, V. P.; Sokol, V. I.; Fogel’zang, A. E.; Serushkin, V. V.;
Porai-Koshits, M. A.; Svetlov, B. S. The vibrational Spectra and
structure of coordination compounds of metals with 4-amino-1,2,4-
triazole as bidendate ligand. Russ. J. Inorg. Chem. 1987, 32, 1950−1955.
(22) Haasnoot, J. G.; Groeneveld, W. L. 1,2,4-Triazole complexses,
III complexes of transition metal(II) nitrate and fluoroborates. Z.
Naturforsch. 1977, 32b, 533−536.
(23) If samples of both colors were not stable at RT or a pink color
rather than purple color was obtained, the sample was dehydrated and
magnetic properties were difficult to observe. To rehydrate the sample,
cotton soaked with a small volume of water was placed in the tube
over the powder.
(24) The pellet heated at 340 K was white but became at RT slightly
pinkish as revealed by an absorbance different from the diffusion
baseline in Figure 6. The KBr pelleting probably induces a
modification of thermochromic properties (position or width of
hysteresis) compared with those obtained for the pure compound in
the solid state. This effect gave the opportunity to speak about
complex limitations for an industrial development
(25) Hauser, A.; Gütlich, P.; Goodwin, H. A. Ligand Field Theoretical
Considerations Spin Crossover in Transition Metal Compounds I;
Springer: Berlin/Heidelberg, 2004; Vol. 233, pp 49−58.
(26) The band corresponding to this transition is very broad and not
very intense. It can be observed only by recording a reflectance diffuse
spectra of the solid. The spectra is provided in Supporting
Information.
(27) Bower, N.; Yu, A. Exploiting mass measurements in different
environments: density, magnetic susceptibility, and thermogravimetry.
J. Chem. Educ. 2011, 88, 536−539. This publication can be used to
correlate a color to magnetic property (dia- or paramagnetic). In this
case, magnetic data storage could be introduced.

1076 dx.doi.org/10.1021/ed4000487 | J. Chem. Educ. 2013, 90, 1071−1076

 PRÁCTICA 5
Síntesis y caracterización de complejos metálicos luminiscentes derivados
de iones lantánidos de Tb(III) y Eu(III).
1.1.- Síntesis de los complejos metálicos [Tb(tmh)3(bipy)] y
[Eu(tta)3(bipy)2].

1.2.- Caracterización de los complejos. Estudio de sus propiedades ópticas

y luminiscentes. Construcción de un diagrama de energía.
1.1.a- Síntesis del complejo metálico [Tb(tmh)3(bipy)2].
Using a graduated cylinder measure out 7.5 mL of absolute ethanol and place it
in a 250 mL beaker. Weigh out 2.1 mmoles of 2,2,6,6-tetramethyl-3,5-heptanedione
(Htmh) and add it to the beaker containing the absolute ethanol. With a graduated
cylinder measure out approximately 2.1 mmoles of 0.1 M sodium hydroxide and add
this drop wise to the Htmh solution. In a separate 25 mL beaker add 7.5 mL of absolute
ethanol, using a graduated cylinder. To this absolute ethanol, add 0.7 mmoles of 2,2’-
bipyridine (bipy) and stir the solution until the bipy is dissolved. Once the 2,2’-
bipyridine is dissolved pour this solution into the Htmh solution, add a stir bar, place the
beaker on a stir plate and mix the solution for 30 minutes. While this solution is stirring
take a 10 mL beaker and add 5.0 mL of distilled water using a graduated cylinder. To
this beaker and 0.7 mmoles of Terbium(III) chloride hexahydrate and swirl gently until
the europium salt is dissolved. After 30 minutes, add the Terbium(III) chloride solution
drop wise using a disposable Pasteur pipette to the stirring ligands solution. A
precipitate should begin to form almost immediately. After all the europium chloride
solution has been added allow the mixture to stir an additional 5 minutes. Vacuum filter
the solution using a Büchner funnel and wash the precipitate three times with 10 mL of
cold water. Transfer the product to a watch glass and allow it to air dry until the next
period.

1.1.b- Síntesis del complejo metálico [Eu(tta)3(bipy)2].

Using a graduated cylinder measure out 7.5 mL of absolute ethanol and place it
in a 250 mL beaker. Weigh out 2.1 mmoles of 4,4,4-trifluoro-1-(2-thienyl)-1,3-
butanedione (Htta) and add it to the beaker containing the absolute ethanol. With a
graduated cylinder measure out approximately 2.1 mmoles of 0.1 M sodium hydroxide
and add this to the Htta solution. In a separate 25 mL beaker add 7.5 mL of absolute
ethanol, using a graduated cylinder. To this absolute ethanol, add 0.7 mmoles of 2,2’-
bipyridine (bipy) and stir the solution until the bipy is dissolved. Once the 2,2’-
bipyridine is dissolved pour this solution into the Htta solution, add a stir bar, place the
beaker on a stir plate and mix the solution for 30 minutes. While this solution is stirring
take a 10 mL beaker and add 5.0 mL of distilled water using a graduated cylinder. To
this beaker and 0.7 mmoles of Europium(III) chloride hexahydrate and swirl gently until
the europium salt is dissolved. After 30 minutes, add the europium(III) chloride solution
drop wise using a disposable Pasteur pipette to the stirring ligands solution. A
precipitate should begin to form almost immediately. After all the europium chloride
solution has been added allow the mixture to stir an additional 5 minutes. Vacuum filter
the solution using a Büchner funnel and wash the precipitate three times with 10 mL of
cold water. Transfer the product to a watch glass and allow it to air dry until the next
period.
1.2.- Caracterización del complejo [Eu(tta)3(bipy)]. Estudio de sus
propiedades ópticas y luminiscentes. Construcción de un diagrama de
energía.
1.2.1.- Propiedades ópticas y luminiscentes.

1.2.1.1.- Espectroscopía UV-Vis de los complejos [Eu(tta)3(bipy)] y

[Tb(tmh)3(bipy)]. En un vaso de precipitado de 50 mL añadir una pequeña cantidad del
complejo previamente sintetizado (aproximadamente 1 – 2 mg) y añadir
aproximadamente 25 mL de metanol. Agitar hasta que todo el sólido se disuelva.
Transferir parte de esta disolución a una cubeta de cuarzo hasta completar
aproximadamente 4/5 de su capacidad. Colocar la cubeta en el espectrofotómetro (en el
que ya se ha medido la línea base) y realizar un espectro en el intervalo de longitudes de
onda comprendido entre 200 – 600 nm. Determinar las longitudes de onda a la que
aparecen los máximos de absorción. Estos valores indicarán la longitud de onda de
excitación que hemos de utilizar para medir el espectro de emisión. Este valor de
absorbancia representa la energía de la transición desde el estado fundamental S0 al
primer nivel excitado S1 en el ligando de tipo dicetona. (nota: no se necesitan conocer
los coeficientes de extinción molar por lo que no es necesario conocer de manera
exacta la concentración de complejo. Puede ser necesario diluir varias veces la
solución preparada hasta obtener un espectro óptico donde el valor máximo de
absorbancia sea inferior a 1.5. Valores de absorbancia superiores a 2 dan lugar a
espectros con mucho ruido de fondo).

1.2.1.2.- Luminiscencia de los complejos [Eu(tta)3(bipy)] y [Tb(tmh)3(bipy)].

El espectro de emisión de este complejo se realizará sobre la disolución

preparada en el apartado 1.2.1.1 y también sobre muestra sólida. La longitud de onda de
excitación coincidirá con el máximo de absorbancia medido anteriormente. El espectro
de emisión se medirá en el intervalo comprendido entre 400 y 800 nm.

1.2.1.2.- Luminiscencia de los ligandos Htta y Htmh.

Para conocer la energía del estado triplete (3T1) del ligando Htta se disolverán
aproximadamente 1 – 2 mg de ligando en 25 – 40 mL de metanol y se medirá su
espectro de emisión en el intervalo 350 – 500 nm utilizando como longitud de onda de
excitación la misma que para el complejo derivado.
 A partir de los datos obtenidos con estos espectros, se construirá el diagrama de
energía correspondiente.
 In the Laboratory

Synthesis and Characterization of Europium(III)

and Terbium(III) Complexes: An Advanced
Undergraduate Inorganic Chemistry Experiment
Shawn Swavey
Department of Chemistry, University of Dayton, Dayton, Ohio 45469-2357
Shawn.swavey@notes.udayton.edu

Descriptions of the f-block metals is typically reserved for

the end of most inorganic courses and often only briefly covered
in a typical one-semester advanced course. There are a limited
number of undergraduate experiments involving lanthanide
coordination complexes (1). This is unfortunate given the ease
with which many of these complexes can be made, the interesting
and instructive photophysical properties, and the relatively
inexpensive starting materials. In the classroom, the term sym-
bols and their use in describing spectroscopic properties is usually
relegated to the d-block metals; however, laboratory illustrations
of the link between theory and experiment are often difficult to
solidify in the minds of the students. Lanthanide coordination
complexes make this link with little need to introduce new Figure 1. Illustrations of the effect of irradiation, using a UV light box of
concepts; students can take what they have learned in the Tb(tdh)3bpy and Eu(tdh)3bpy complexes.
classroom with respect to microstates and term symbols and
apply these principles to the f orbitals associated with lanthanide Scheme 1. Synthetic Scheme of 2,20 -Bipyridine-bis{tris[2,2,6,6-tetra-
complexes. methyl-3,5-heptanedione]}-lanthanide(III): Tb(tmh)3bpy and Eu-
Compared to transition-metal coordination complexes, the (tmh)3bpy
area of lanthanide coordination chemistry is a relatively young field.
A number of advances in this area have been made in recent years
with applications in catalysis (2), biosensors (3), and light-emitting
materials (4) to name just a few. Stabilization of the diffuse 4f
orbitals leads to an open-shell electronic configuration in which the
lanthanides favor the þ3 oxidation state. Lanthanide(III) cations
display typical a-class (hard) properties; therefore, coordination is
accomplished by strong Lewis bases and in particular bidentate
ligands containing oxygen or nitrogen (5). Charged oxygen atoms
favor ionic bonding to lanthanides. Metal-metal charge-transfer Tb(III) complexes. The synthesis of Tb(III) and Eu(III) com-
transitions of the 4f electrons into the 4f* excited state are plexes (7) is illustrated in Scheme 1. In this synthetic scheme,
forbidden by the selection rules. To circumvent these forbidden the β-diketone 2,2,6,6-tetramethyl-3,5-heptanedione (tmh), 2,20 -
transitions, “antenna” ligands are used to absorb energy in the UV bipyridine (bpy), and terbium(III) chloride or europium(III)
region of the spectrum transferring that energy to the lanthanide chloride are combined to make the complex 2,20 -bipyridine-bis-
metal inducing a 4f-4f* (ligand field) transition. Relaxation of the {tris[2,2,6,6-tetramethyl-3,5-heptanedione]}-lanthanide(III),
excited 4f electrons to the ground state leads to emission spectra in Ln(tmh)3bpy. Because of the large lanthanide cations, higher
the visible and near-infrared regions of the spectrum. The high coordination numbers are typically observed; for example,
degree of spin-orbit coupling associated with lanthanides leads to Tb(tmh)3bpy and Eu(tmh)3bpy (Scheme 1) are eight coordi-
intense ligand-field emissions. Excellent coordination and energy- nate with six oxygen atoms from three tmh ligands and two
transfer ligands, for example, β-diketonates, have been identi- nitrogen donors from the 2,20 -bpy ligand.
fied (6). Europium(III) and terbium(III) are instructively interest- The addition of 2,20 -bipyridine displaces coordinated water
ing owing to their sharp long-lived emission lines lying in the visible molecules, which deactivate the metal emission through OH
region of the spectrum. For example, terbium(III) complexes vibrations. The presence of C-H bonds leads to vibrational
excited with UV light emit green light, whereas europium(III) quenching of the lanthanide emission. To avoid this mechanism
complexes excited with UV light emit yellow or red light (Figure 1). of deactivation, some of the β-diketones chosen contain heavier
It should be noted that emissions of the complexes in solution are C-F bonds. The β-diketones are stirred in a basic ethanolic
similar to those in the solid state. solution to ensure the enol form before addition of the lantha-
We have identified a series of inexpensive and readily nide salt. In this experiment, the synthesis of two terbium(III)
available reagents that can be used to synthesize Eu(III) and and two europium(III) complexes incorporating 2,20 -bipyridine

_ _ _
r 2010 American Chemical Society and Division of Chemical Education, Inc. pubs.acs.org/jchemeduc Vol. 87 No. 7 July 2010 Journal of Chemical Education 727
10.1021/ed100188m Published on Web 05/03/2010
 In the Laboratory
Figure 2. Excitation and emission spectrum of Tb(tdh)3bpy.
and either europium(III) chloride or terbium(III) chloride and
three β-diketones [1,1,1,-trifluoro-5,5-dimethyl-2,4-hexanedione
(tdh), 2,2,6,6-tetramethyl-3,5-heptanedione (tmh), and thenoyl-
trifluoroacetone (tta)] are described. Their spectroscopic and
fluorescence properties are measured and used to create energy
diagrams for each complex.
Experiment and Discussion
The preparation of the Tb(III) and Eu(III) complexes
[Tb(tmh)3bpy, Eu(tmh)3bpy, Tb(tdh)3bpy, and Eu(tta)3bpy] is
accomplished in one 3-h laboratory by the addition of an aqueous
solution of the respective lanthanide salt to a basic ethanolic solu-
tion containing the respective β-diketone and 2,20 -bipyridine.
(Note: If desired, all three ligands can be used for both Tb(III) and
Eu(III) giving a total of six complexes.) Precipitation of the
products occurs immediately. After vacuum filtering and air drying
until the next laboratory period, the europium complexes can be
isolated as a pale-yellow powder, whereas the terbium complexes
are isolated as a green powder. The π-π* transitions of the
β-diketonate ligands are measured by dissolving a small quantity of
each complex in methanol and scanning from 200 to 400 nm with
the UV-vis spectrophotometer. The 4f-4f* (ligand field) transi-
tions of the metals are forbidden and therefore not observed
in these measurements; however, the single intense absorption
bands observed in the UV region of the spectrum for each complex
can be associated with the S0 f S1 (π-π*) transition of the
β-diketonate. The peak absorption wavelength measured is also
the wavelength at which the associated complex will be excited in
the fluorescence experiments.
Solid-state fluorescence studies of the four metal com-
plexes is accomplished by placing the powder of the complex of
interest into a quartz fluorescence cuvette and photoexciting
the complex at the wavelength that corresponds to the π-π*
transition of the β-diketonate (determined by the UV-vis
experiments). Absorption of the 2,20 -bipyridyl ligand occurs at
a higher energy than the β-diketonate ligand and with much
lower intensity considering there is only one bipyridine and
three β-diketones per complex. For this reason, energy transfer
comes primarily from the β-diketonate ligand. Scanning the
visible region reveals an emission spectrum associated with
the lanthanide metal. For example, Tb(III) has a ground-state
electronic configuration of [Xe]4f8 with six unpaired electrons.
This configuration leads to a 7FJ ground state with spin-orbit
coupling J = 0, 1, 2, 3, 4, 5, 6 corresponding to seven possible
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Figure 3. Energy-level diagram for the Tb(tdh)3bpy complex in Figure 2.
Arrows indicate the course of energy transfer during excitation by UV
radiation and emission of visible light. The ground and excited states of
the bpy ligand are not included because they play a relatively small role
in the energy-transfer process.
transitions, with 6 lines distinguishable in the emission spec-
trum as illustrated in Figure 2 for a Tb(III)-β-diketonate
complex. For Tb(III), the first excited state can be described as a
5
D4 state and its energy corresponds to the transition to the
lowest ground state, 5D4 f 7F6 (Figure 2). The difference in
energy between the 5D4 f 7F6 and the 5D4 f 7F5 allows for
calculation of the energy of the 7F5 state. The energies of the
other various states can be calculated in a similar manner. Once
the electronic states of the terbium(III) center along with the S0
and S1 states of the respective β-diketonates have been deter-
mined, the triplet T1 states of the β-diketonates are determined
by fluorescence measurements of the lone ligands in solution.
An energy diagram for each complex, similar to the one in
Figure 3, can be constructed from the information gathered in
the spectroscopic analyses. It may be instructive for students in
the class to pool their results for comparative purposes.
To determine the term symbols associated with a particular
metal ion one must consider its electronic configuration. For
example, europium(III) has an [Xe]4f 6 ground-state electron
configuration that, similar to Tb(III), has six unpaired electrons
in the 4f orbitals.
The total orbital angular momentum quantum number L and
therefore the ground-state term for this configuration is the sum
of the ml values,
L ¼ fð þ 3Þ þ ð þ 2Þ þ ð þ 1Þ þ ð0Þ þ ð - 1Þ þ ð - 2Þg ¼ 3
and L = 3 corresponds to an F state. The total spin-angular-
momentum quantum number S and therefore the spin state for
the ground term are equal to the sum of the ms values,
S ¼ fð1=2Þ þ ð1=2Þ þ ð1=2Þ þ ð1=2Þ þ ð1=2Þ þ ð1=2Þg ¼ 3
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and S = 3 gives a spin state 2S þ 1 = 7. Spin-orbit coupling
determines how the ground term splits into different energies
and is determined by:
J ¼ L þ S, L þ S - 1, L þ S - 2, :::, jL - Sj
For L = 3 and S = 3, J takes on the values of 6, 5, 4, 3, 2, 1, 0.
Therefore, the ground-state septet F term for Eu(III) is split as
follows:
This splitting indicates that the Eu(III) complex should have
seven emission lines in the fluorescence spectrum. The first
excited state for the Eu(III) configuration is the 5D0 state with
the ground-state configuration of 7FJ (J = 0, 1, 2, 3, 4, 5, 6).
Because the 4f orbitals in Eu(III) are half-filled, the order of the
ground-state energies is the reverse of the Tb(III) ground-state
F term (i.e., 7F0 is the lowest energy in the Eu(III) case, whereas
7
F6 is the lowest energy for Tb(III), Figure 3). From Hund's third
rule, for subshells that are less than half-filled, the state having
the lowest J value has the lowest energy; for subshells that are
more than half-filled, the state having the highest J value has the
lowest energy (8). The S0, S1, and T1 states will depend on the
β-diketonate used. It is important for the students to recognize
any difference in emission intensities and see if they can relate the
intensity differences to the energy differences between the triplet
state of the ligand and the excited state of the metal. The 2,20 -
bipyridyl ligand is not included in the energy diagram because the
π-π* transitions associated with this ligand are too high in
energy to be involved with energy transfer to the metal; again, the
students should be reminded that the purpose of the 2,20 -
bipyridyl ligand is to enhance the luminescence intensity by
preventing OH quenching from coordinated water molecules.
Hazards
Methanol is flammable and an irritant. 2,20 -Bipyridine and
thenoyltrifluoroacetone are harmful if swallowed and cause irrita-
tion to skin, eyes, and respiratory tract. They also have strong odors
and should be handled in the fume hood. Although the other
reagents may be handled outside of the hood, gloves and eye
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r 2010 American Chemical Society and Division of Chemical Education, Inc.
In the Laboratory
protection should be worn at all times. 2,2,6,6-Tetramethyl-3,5-
heptanedione is a combustible liquid and vapor and causes eye,
skin, and respiratory tract irritation. 1,1,1,-Trifluoro-5,5-dimethyl-
2,4-hexanedione is flammable and is an irritant. Europium chloride
and terbium chloride are hygroscopic and irritants. Sodium hydro-
xide is corrosive. Ethyl alcohol is flammable.
Conclusions
The experiments described here are ideally suited to accom-
pany an advanced undergraduate inorganic chemistry course and
would be best performed after microstates, spin-orbit coupling,
and term symbols are discussed in the lecture. From purely a
synthetic point, this laboratory can be easily adapted for the
general chemistry laboratory; however, with very large sections, it
could become expensive. The use of different β-diketonates with
varied absorption maxima gives the student examples of the role
that the ligand plays in the energy-transfer process. It is expected
that this will be discussed in the student's final report. I require
that the students' reports mirror those of an ACS journal with
title, abstract, experimental procedures, results and discussion,
conclusions, and reference sections. Obviously, this example does
not need to be followed for this laboratory to be successful. The
time required for the students to analyze their data is sufficient to
reap the benefits of this laboratory.
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Supporting Information Available
Student handout; pre- and postlab questions; instructor information;
answers to the pre- and postlab questions. This material is available via the
Internet at http://pubs.acs.org.
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