FULL PAPER
DOI: 10.1002/ejic.201100131
Aminotroponiminate and Aminotroponate Complexes of Group 15 (P, As)
Elements: Synthesis, X-ray Diffraction Analysis and Reactivity
Lucian-Cristian Pop,[a,b] Annie Castel,*[a] Luminita Silaghi-Dumitrescu,*[b] and
Nathalie Saffon[c]
Keywords: Phosphorus / Arsenic / N,N ligands / N,O ligands / Cycloaddition / Tungsten
New phosphenium and arsenium cations stabilized by biden-
tate monoanionic N-isopropyl-2-(isopropylamino)troponim-
inate or 2-(isopropylamino)troponate units have been synthe-
sized. These complexes were characterized by 31P, 1H and
13
C NMR spectroscopy and the molecular structures were de-
termined by X-ray crystallography. These data indicate the
formation of N,N⬘- and N,O-chelate derivatives with three-
coordinate Group 15 atoms included in planar heterobi-
Introduction
Aminotroponiminates ([ATI]–) are a well-known class of
ligands that have found extensive use in coordination chem-
istry leading to a large number of transition-metal and
main-group complexes.[1] On the one hand, this ligand dis-
plays heteroatom bonding and a highly conjugated 10π elec-
tron system that should allow charge delocalization when
incorporating the pnictogenium atom into the π electron
backbone. On the other hand, and in marked contrast to
the β-diketiminate scaffold, [ATI]– is expected to form
stable five-membered chelate rings and its anticipated fused
ring structure should disfavour side-reactions. In contrast,
aminotroponates ([AT]–), which may formally be considered
as a combination of amido and carbonyl donors, have been
much less investigated.[2] However, the coordination chemis-
try of both these ligand types with Group 15 divalent ele-
ments remains totally unexplored. Pnictogenium cations,
[a] Laboratoire Hétérochimie Fondamentale et Appliquée, UMR/
CNRS 5069, Université Paul Sabatier,
118, Route de Narbonne, 31062 Toulouse Cedex 9, France
Fax: +33-5-61558204
E-mail: castel@chimie.ups-tlse.fr
[b] Babes-Bolyai University,
1, Kogalniceanu Street, Cluj-Napoca, Romania
Fax: +40-264-59-19-06
E-mail: lusi@chem.ubbcluj.ro
[c] Structure Fédérative Toulousaine en Chimie Moléculaire
(FR2599), Université Paul Sabatier,
118, Route de Narbonne, 31062 Toulouse Cedex 9, France
Eur. J. Inorg. Chem. 2011, 3357–3364 © 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
cycles. The reactivities of these cationic species were investi-
gated. The phosphenium cations were found to be more reac-
tive than their arsenium analogues, especially towards an o-
quinone, with the formation of a phosphate ester derivative.
Complexation reactions with [(THF)W(CO)5] afforded the
first aminotroponiminato hydroxyphosphenium cation stabi-
lized by coordination to a transition metal.
like other low-coordinate Group 15 elements, are conspicu-
ous by virtue of their expected ambiphilic (Lewis acid and
base) properties. They are six-electron dicoordinate
Group 15 species and are isovalent analogues of carbenes.
The stability of these species depends on charge delocaliza-
tion through heteroatom bonding and/or by incorporation
of the pnictogen atom into a conjugated π system. Among
the numerous types of pnictogenium cations that have been
prepared and studied,[3] the most important class is that
analogous to N-heterocyclic carbenes that display two nor-
mal covalent E15–N bonds (E15 = P,[4] As,[5] Sb[4c,5b,6]).
More recently, some species having amino/imino ligands
with a covalent E15–N bond and a coordinative E15씮N
bond have been reported. In this context, Cowley and co-
workers synthesized the first example of a phosphenium
cation stabilized by the N,N⬘-chelation of a β-diketiminato
ligand, which can be regarded as an intramolecular donor
adduct.[7] Surprisingly, only a few Group 15 element com-
plexes of this type have been described,[8] whereas a large
number of intermolecular donor adducts of both phos-
phenium[3a,9] and arsenium[10] cations are known. As part
of our ongoing investigation of main-group elements in un-
usually low oxidation states, we have recently shown that
chlorophosphenium cations can be stabilized by aminotro-
poniminate and aminotroponate ligands.[11] In this paper,
we report an extension of this work to the N,N- and N,O-
chelated stabilization of the arsenic element. Some reac-
tions, namely oxidative cycloaddition with an o-quinone
and complexation with a transition-metal complex, will be
also described.
3357

FULL PAPER
Results and Discussion
Synthesis, NMR Spectroscopy and Structural Studies of
Pnictogenium Cations 1–4
In previous work,[11] we have shown the impact of the
synthetic process on the nature of the product obtained
when phosphorus bears an aminotroponiminato substitu-
ent. Indeed, the nucleophilic substitution reaction of PCl3
and the monolithiated ligand gave a mixture of dissociated
and non-dissociated forms 1a and 1b whereas the base-in-
duced dehydrochlorination coupling reaction selectively
yielded the phosphenium cation 1a (Scheme 1).
Scheme 1.
The analogous arsenic system is more complex because
only one form (2 or 3) was obtained regardless of the exper-
imental conditions used and the nature of the ligand
(Scheme 2). These compounds were isolated as yellow solids
in 50–60 % yields. Note that the N,O-chelated product 3 is
more unstable than the N,N⬘-chelated analogue 2, particu-
larly in solution, leading to the formation of aminotropone.
Scheme 2.
The 1H NMR spectra of compounds 2 and 3 exhibit res-
onances for the ring protons that are significantly shifted
downfield (Δδ ≈ 1.0 ppm) relative to those of the starting
ligands, presumably because of the increased conjugation of
π electrons in the newly formed metallacycles. A similar ef-
fect, but more pronounced, has already been observed for
the phosphenium cation 1a. The spectroscopic data indicate
the possible existence of dissociated forms. To gain more
insight into their structures, we performed X-ray diffraction
analysis. Single crystals of compound 2 were isolated by
very slow crystallization from a dichloromethane solution
3358 www.eurjic.org © 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
L.-C. Pop, A. Castel, L. Silaghi-Dumitrescu, N. Saffon
at –30 °C. The molecule crystallizes in the monoclinic
P21/c space group with one H2O molecule per molecule of 2
(Figure 1). The aminotroponiminato ligand chelates to the
arsenic centre with near perfect planarity of the two cycles.
The most noteworthy structural feature concerns the As–
Cl bond lengths, which differ significantly [2.3759(4) and
2.7974(6) Å]. The first value is in the range of As–Cl cova-
lent bond lengths observed in the related compound
ClAs(tBuNCH2CH2NtBu) [2.375(2) Å][4a] and ClAs(iPrN)2-
C10H6 [2.2820(8) Å].[4c] In contrast, the second is much
elongated and is in the range of the bridging As–Cl bonds
observed in chlorodiarsenate Ph4P[As2Cl8]·CH3CN (2.639
and 3.042 Å).[12] However, the corresponding chloride atom
is hydrogen-bonded to the H2O molecule with a distance of
3.209 Å for the Cl···H(O) interaction. The presence of such
an interaction could have an effect on the As–Cl bond
length. Accordingly, it was of interest to examine the struc-
ture of an arsenium salt that does not present hydrogen
bonding.
Figure 1. Molecular structure of 2 (50 % probability level for the
thermal ellipsoids) with hydrogen atoms and solvent molecules
omitted. Selected bond lengths [Å] and angles [°]: As1–N1
1.8445(12), As1–N2 1.8502(12), As1–Cl1 2.3759(4), As1–Cl2
2.7974(6), N1–C1 1.3611(17), N2–C2 1.3585(18), C1–C7 1.398(2),
C1–C2 1.448(2), C2–C3 1.400(2), C3–C4 1.385(2), C4–C5 1.381(2),
C5–C6 1.378(2), C6–C7 1.386(2); N1–As1–N2 84.28(5), N1–As1–
Cl1, 95.37(4), N2–As1–Cl1 96.46(4), N1–As1–Cl2, 88.26(4), N2–
As1–Cl2 91.16(4), Cl1–As1–Cl2 171.85(1), C1–N1–As1 115.53(9),
C2–N2–As1 115.58(10).
The triflate salt 4 was easily prepared from 2 by chloride
abstraction using trimethylsilyl triflate (Me3SiOTf,
OTf=OSO2CF3; Scheme 2). As expected, the 1H NMR
spectrum shows a more pronounced deshielding of the ring
protons (Δδ ≈ 1.5 ppm) compared with in the starting li-
gand. Its molecular structure (including selected bond
lengths and angles) is shown in Figure 2. Compound 4
shows the same general features as phosphenium cation 1[11]
consisting of separated ion-pairs with triflate as the anion.
The nearest distance between the ions is F–···H(cation)
(2.73 Å). The shortest distance between the anion and the
arsenic atom is 6.91 Å. The cationic part is formed by the
AsCl unit, which is stabilized by the chelating ligand sys-
tem. The three-coordinate arsenic atom adopts a pyramidal
geometry (sum of the angles is 282.8°) with the bonded
Eur. J. Inorg. Chem. 2011, 3357–3364
Aminotroponiminate and Aminotroponate Complexes
chloride atom in an approximately orthogonal position with
respect to the heterobicyclic plane. The As–N bond lengths
[As–N1 = 1.837(4), As–N2 = 1.840(4) Å] are similar to
those reported for a five-membered aromatic arsenium cat-
ion [1.8377(14) and 1.8271(13) Å].[5b] Likewise, the C–C
and C–N bond lengths are only marginally different, which
suggests an almost similar degree of delocalization of the
electrons in the systems.
Figure 2. Molecular structure of 4 (50 % probability level for the
thermal ellipsoids). All H atoms have been omitted for clarity. Se-
lected bond lengths [Å] and angles [°]: As1–N1 1.837(4), As1–N2
1.840(4), As1–Cl1 2.2808(15), N1–C1 1.356(5), N2–C2 1.360(5),
C1–C7 1.396(6), C1–C2 1.447(6), C2–C3 1.396(6), C3–C4 1.385(6),
C4–C5 1.393(7), C5–C6 1.371(7), C6–C7 1.390(7); N1–As1–N2
84.77(16), N1–As1–Cl1, 99.44(12), N2–As1–Cl1 98.63(12), C1–
N1–As1 115.5(3), C2–N2–As1 114.9(3).
Interestingly, compound 3 adopts a very different struc-
ture. In the solid state, the neutral dichloroarsine unit pres-
ents a dimeric arrangement involving a four-membered
As2Cl2 ring (Figure 3). The asymmetric unit contains two
chemically similar but crystallographically different dimers
of 3. The main difference lies in the As–Cl distances. The
As–Cl distances [2.7221(7) and 2.8740(7) Å, 2.7222(8) and
2.9884(5) Å] of the As2Cl2 parallelogram are significantly
elongated compared with those of the exocyclic As–Cl
bonds [2.3202(6) and 2.3088(8) Å], which are in the range
of covalent As–Cl bonds.[4a,4c] Similar halogen-bridged ar-
rangements have been reported for chloroarsenic com-
pounds such as chlorobenzothiazarsole,[13] chloroarsines,[14]
and chlorodiarsenates.[12] The heterobicyclic unit is planar
and perpendicular to the As2Cl2 system. The As–O bond
lengths [1.8194(16) and 1.8150(16) Å] are close to that of a
single bond (1.78 Å)[15] and the As–N distances [1.9250(16)
and 1.9208(19) Å] are elongated compared with those in 4,
which confirms a strong interaction between the arsenic
atom and the chelating system even in the case of the non-
dissociated form.
Eur. J. Inorg. Chem. 2011, 3357–3364 © 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Figure 3. Molecular structure of the dimeric unit of compound 3
(50 % probability level for the thermal ellipsoids) with hydrogen
atoms omitted. The two independent molecules of the asymetric
unit are shown. Selected bond lengths [Å] and [°]: As1–O1
1.8194(16), As1–N1 1.9250(17), As1–Cl1 2.3202(6), As1–Cl3
2.7721(7), As1–Cl3A 2.8740(7), N1–C1 1.333(3), O1–C2 1.348(3),
C1–C7 1.420(3), C1–C2 1.446(3), C2–C3 1.365(3), C3–C4 1.404(3),
C4–C5 1.371(3), C5–C6 1.393(3), C6–C7 1.373(3); O1–As1–N1
83.56(7), O1–As1–Cl1 93.76(5), N1–As1–Cl1 93.24(6), C1–N1–As1
114.19(14), C2–O1–As1 115.97(13), O1–As1–Cl3 84.91(5), N1–
As1–Cl3 87.28(6), O1–As1–Cl3A 81.81(5), N1–As1–Cl3A
165.36(6), Cl1–As1–Cl3 88.41(2), Cl1–As1–Cl3A 178.51(3), Cl3–
As1–Cl3A 90.73(2); As2–O2 1.8150(16), As2–N2 1.9208(19), As2–
Cl2 2.3088(8), As2–Cl4 2.7222(8), As2–Cl4A 2.9884(5), N2–C11
1.337(3), O2–C12 1.344(3), C11–C17 1.418(3), C11–C12 1.437(3),
C12–C13 1.382(3), C13–C14 1.398(3), C14–C15 1.364(4), C15–C16
1.401(4), C16–C17 1.367(3); O2–As2–N2 84.00(8), O2–As2–Cl2
92.62(6), N2–As2–Cl2 93.28(6), C11–N2–As2 113.54(15), C12–O2–
As2 115.54(14), O2–As2–Cl4 86.05(6), N2–As2–Cl4 87.49(6), O2–
As2–Cl4A 81.94(6), N2–As2–Cl4A 164.91(6), Cl2–As2–Cl4
178.39(3), Cl2–As2–Cl4A 92.83(3), Cl4–As2–Cl4A 86.08(2).
Reactivity of Pnictogenium Cations
It is well known that phosphenium cations act like dieno-
philes with 1,3-dienes.[3a] However, neither phosphenium
cation 1a nor the arsenium derivative 2 react with dimethyl-
butadiene, whatever the experimental conditions used (in
dichloromethane solution[16] or in a sealed tube at
100 °C[17]). In contrast, an immediate reaction was observed
between phosphenium cation 1a and 3,5-di-tert-butyl-1,2-
benzoquinone at room temperature, however, the arsenium
2 failed to react.
The dropwise addition of the o-quinone to a solution of
compound 1a in CH2Cl2 caused an immediate discoloration
of the quinone solution. The reaction was monitored by 31P
NMR, which showed the formation of a single product (δ
= 7.83 ppm), identified as 5, that was easily isolated after
evaporation of the solvent (Scheme 3). Compound 5 is very
sensitive to moisture in solution and rapidly gives the phos-
phate ester 6, which is the tautomeric form of hydroxyphos-
phorane ⬎P(OH)O–.[18] Slow crystallization in CH2Cl2 at
www.eurjic.org 3359

FULL PAPER
–30 °C gave suitable crystals for X-ray analysis (Figure 4).
No interaction was detected between the phosphorus atom
and the chloride anion (P+···Cl–, 3.920 Å) and the two fused
cycles (five- and seven-membered rings) are almost in the
same plane. The phosphorus atom is tetracoordinate. The
P–O bond length [1.568(3) Å] lies between a typical P–O
single bond (1.71 Å) and a P=O double bond (1.40 Å).[19]
The P=O bond length [1.456(3) Å] is very close to the value
of a standard P=O double bond. The dioxygenated phenyl
system lies in a plane perpendicular to the cationic part to
reduce steric constraints.
Scheme 3.
DFT calculations were performed on phosphenium[11]
and arsenium cations.[20] They revealed a high-lying phos-
phorus lone-pair orbital (HOMO–1) which should allow an
easy coordination of phosphenium cations to metal car-
bonyl fragments. In contrast, the arsenic lone-pair resides
in the HOMO–4 and seems to be less accessible for metal
complexation. This proved to be the case during its reaction
with [W(CO)5THF] as no arsenium complex could be char-
acterized or isolated. In contrast, stoichiometric amounts
of phosphenium cation 1a and complex [W(CO)5THF] in
THF at room temperature easily led to the transient chloro
complex identified by 31P NMR spectroscopy (δ =
150.03 ppm). This latter rapidly hydrolysed to give the hy-
droxy complex 7 (Scheme 4). The 31P NMR spectrum
shows a signal at δ = 128.65 ppm accompanied by satellites
of tungsten with a coupling constant JWP = 386 Hz. This
value is close to that observed for the similar complex
Scheme 4.
3360 www.eurjic.org © 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
L.-C. Pop, A. Castel, L. Silaghi-Dumitrescu, N. Saffon
Figure 4. Molecular structure of 6 (50 % probability level for the
thermal ellipsoids). All H atoms (except H3) and solvent molecules
have been omitted for clarity. Selected bond lengths [Å] and angles
[°]: P1–O1 1.456(3), P1–O2 1.568(3), P1–N1 1.667(4), P1–N2
1.669(4), N1–C1 1.384(5), C1–C7 1.380(6), C1–C2 1.440(6), C2–
C3 1.407(6), C3–C4 1.375(6), C4–C5 1.382(6), C5–C6 1.381(6), C6–
C7 1.384(6); O1–P1–O2 115.05(18), O1–P1–N1 120.62(18), O2–P1–
N1 101.95(18), O1–P1–N2 115.43(19), O2–P1–N2 108.67(18), N1–
P1–N2 92.20(19), C1–N1–P1 113.2(3), C2–N2–P1 113.1(3).
[{(C5Me5)(tBuNH)P}W(CO)3(MeCN)2]+ AlCl4– (404 Hz),[21]
but smaller than that reported for the W=P double bond in
[Cp(CO)2W=P{OC(CH3)2C(CH3)2O}] (847 Hz),[22] results
that suggest a small amount of π character in the W–P
bond.
The 13C NMR spectrum shows two sharp resonances at
low field of relative intensity 4:1 belonging to the equatorial
and axial carbonyl groups that are split by C–P coupling: δ
= 195.20 (2JC,P = 9.3 Hz) and 196.18 ppm (2JC,P = 8.6 Hz).
The trans carbonyl resonance is slightly deshielded relative
to the cis carbonyl, as previously observed in the literature
for complexes [Y3PW(CO)5] (Y = Me, Bu, Ph, OPh).[23] The
IR spectrum exhibits a pattern characteristic of the
[LW(CO)5][23a] complex with three CO stretching bands at
1833, 1904, and 2017 cm–1.
Slow crystallization in chloroform solution at room tem-
perature gave brown crystals identified as complex 7 by X-
ray analysis (Figure 5). The phosphorus atom is tetracoor-
dinate and the N-heterobicyclic unit is nearly planar and
almost perpendicular to the W(CO)5 system. The long dis-
tance between the phosphorus atom and the chloride anion
Eur. J. Inorg. Chem. 2011, 3357–3364
Aminotroponiminate and Aminotroponate Complexes
[P+···Cl–, 3.833(2) Å] suggests that there is no interaction
between them. The OH group of the cation is hydrogen-
bonded to the chloride anion with a distance of 2.903 Å for
the O1···Cl1 interaction. The P–N bond lengths [1.717(3)
and 1.724(3) Å] are slightly longer than those of 1a
[1.697(1) and 1.708(1) Å]. The P–O bond length
[1.573(3) Å] is in the range of P–OH distances (1.503–
1.611 Å).[24] The tungsten atom is octahedrally coordinated
with an almost linear Cax–W–P angle of 173.33(15)°. The
bond length of P–W [2.4584(9) Å] lies between the P–W
lengths in [W(PCl3)(CO)5] [2.378(2) Å][25] and
[W(PMe3)(CO)5] [2.516(2) Å][25] and is nearly identical to
the P–W bond length [2.460(2) Å] of the hydroxyphosphide
complex [WClCp{PH(OH)R}(CO)2] (R = 2,4,6-
C6H2tBu3).[26]
Figure 5. Molecular structure of 7 (50 % probability level for the
thermal ellipsoids). All H atoms (except H1) have been omitted for
clarity. Selected bond lengths [Å] and angles [°]: P1–O1 1.573(3),
P1–N1 1.717(3), P1–N2 1.724(3), P1–W1 2.4584(9), N1–C1
1.372(4), N2–C2 1.368(5), W1–C16 2.025(5), W1–C18 2.049(5),
O2–C14 1.136(6), O(4)–C16 1.129(6), C1–C7 1.396(5), C1–C2
1.444(5), C2–C3 1.394(5), C3–C4 1.376(6), C4–C5 1.381(6), C5–
C6 1.384(6), C6–C7 1.380(5); O1–P1–N1 105.73(16), N1–P1–N2
88.44(15), C1–N1–P1 114.0(2), C2–N2–P1 113.9(2), O1–P1–W1
107.42(11), N1–P1–W1 123.99(11), N2–P1–W1 122.87(12), C16–
W1–C14 89.05(19), C16–W1–P1 173.33(15).
Compound 7 is the first hydroxyphosphenium cation sta-
bilized both by an intramolecular donor–acceptor bond
and coordination to a transition metal. It is well known
that phosphinous acid (R2POH) is in equilibrium with its
phosphane oxide tautomeric form (R2HP=O) and that this
equilibrium is generally shifted to the phosphane oxide in
the case of the neutral compound.[27] However, phos-
phinous acid can be stabilized by CF3 substituents[28] or by
complexation with a transition metal.[29] In a series of cat-
ionic species, Cowley and co-workers reported the prepara-
tion and characterization of a β-diketiminato hydroxyphos-
phenium.[24b] The preference for the hydroxy tautomeric
form is probably due to the electronic and steric effects of
the N,N⬘-chelating unit. In our case, the presence of the
aminotroponiminato moiety is not sufficient and additional
coordination to tungsten seems to be required for stabiliz-
ing this form.
Eur. J. Inorg. Chem. 2011, 3357–3364 © 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Conclusions
An easy and direct route to the first phosphenium and
arsenium cations stabilized by N,N⬘- or N,O-chelation of a
tropolone scaffold has been described. The presence of a π-
unsaturated backbone in the aminotroponiminate and ami-
notroponate ligands not only prevents the competitive γ-
carbon substitution previously observed for the diketimin-
ate ligand but also allows complete positive charge delocal-
ization onto the seven-membered cycles. This result was
confirmed by spectroscopic studies and X-ray structural
data. The cycloaddition of a phosphenium cation to an o-
quinone with the formation of a phosphate ester derivative
confirms its dienophilic nature. Another interesting feature
is its ability to act as a ligand in the coordination of a tran-
sition-metal complex. A novel cationic tungsten complex,
which is isolobal with transition-metal carbene complexes,
was synthesized and structurally characterized.
Experimental Section
General: All manipulations with air-sensitive materials were per-
formed in a dry and oxygen-free atmosphere of Argon by using
standard Schlenk-line and glove-box techniques. Solvents were
purified with the MBRAUN SBS-800 purification system except
for THF, which was distilled over Na/benzophenone. NMR spectra
were recorded with the following spectrometers: 1H: Bruker Avance
II 300 (300.13 MHz); 13C: Bruker Avance II 300 (75.47 MHz) and
Avance II 500 (100.61 MHz); 31P: Bruker Avance II 300
(121.49 MHz) with H3PO4 as reference; 19F: Bruker Avance 300
(282 MHz) with CFCl3 as reference. Mass spectra were measured
with a Hewlett-Packard 5989A spectrometer in the electron impact
mode (70 eV) and only characteristic fragments are reported. Melt-
ing points were measured with a Leitz microscope or an Electro-
thermal apparatus (capillary). IR spectra were measured with a
Varian 640-IR FTIR spectrometer. Elemental analyses were per-
formed at the Centre de Microanalyse de l’Ecole Nationale Supé-
rieure des Ingénieurs en Arts Chimiques et Technologiques. N-Iso-
propyl-2-(isopropylamino)troponimine, 2-(isopropylamino)trop-
one[30] and the phosphenium cation 1a[11] were prepared according
to literature procedures. The atom labelling used in the NMR as-
signments of 2 is given below:
Synthesis of Dichloroarsine 2
Method 1. By a Dehydrohalogenation Coupling Reaction: AsCl3
(0.36 g, 1.96 mmol) in toluene (5 mL) was added dropwise to a
solution of (iPr2-ATI)H (0.40 g, 1.96 mmol) and Et3N (0.20 g,
1.96 mmol) in toluene (15 mL) over a period of 5 min. The mixture
was stirred for 3 h. After filtration, the volatiles were removed un-
der reduced pressure and the residue was dissolved in CH2Cl2. The
saturated solution was placed in a freezer at –30 °C for 2 d to yield
yellow crystals of 2 (0.34 g, 50 %). M.p. 138–142 °C. 1H NMR
(300 MHz, CDCl3): δ = 1.74 (d, 3JH,H = 6.6 Hz, 12 H, CHCH3),
www.eurjic.org 3361

FULL PAPER
4.40 (sept., 3JH,H = 6.6 Hz, 2 H, CHCH3), 7.24 (t, 3JH,H = 9.6 Hz,
1 H, 5-H), 7.30 (d, 3JH,H = 11.4 Hz, 2 H, 3-H, 7-H), 7.69 (pseudo-
t, 3JH,H = 9.6 Hz, 2 H, 4-H, 6-H) ppm. 13C{1H} NMR (75 MHz,
CDCl3): δ = 21.62 (CHCH3), 51.00 (CHCH3), 121.99 (C-3, C-7),
130.00 (C-5), 139.97 (C-4, C-6), 158.78 (C-2, C-8) ppm. MS (EI):
m/z (%) = 313 (100) [M – Cl]+, 235 (95) [M – 2Cl – iPr]+.
Method 2. By Nucleophilic Substitution Reaction Using an Amino-
lithiated Derivative: A 1.6 m solution of nBuLi in hexanes
(1.60 mmol) was slowly added at 0 °C to a solution of (iPr2-
ATI)H (0.29 g, 1.42 mmol) in diethyl ether (10 mL). The yellow
solution was warmed to room temperature, stirred for 30 min and
slowly added to a cooled (–75 °C) solution of AsCl3 (0.26 g,
1.42 mmol) in diethyl ether (5 mL). The reaction mixture was
warmed to room temperature and stirred for 3 h. After filtration,
the remaining solid was washed with diethyl ether and dried under
vacuum, leading to a yellow powder identified as 2 (0.28 g, 57 %).
Dichloroarsine 3
Method 1. By a Dehydrohalogenation Coupling Reaction: By using
the same procedure as described for 2, from (iPr-AT)H (0.40 g,
2.45 mmol), Et3N (0.25 g, 2.45 mmol) and AsCl3 (0.44 g,
2.45 mmol) in toluene (15 mL) a yellow powder identified as 3 was
obtained. Crystallization from dichloromethane at –30 °C gave 3
as yellow crystals (0.42 g, 56 %). M.p. 106 °C (dec.). 1H NMR
(300 MHz, CDCl3): δ = 1.74 (d, 3JH,H = 6.4 Hz, 6 H, CHCH3),
4.36 (sept., 3JH,H = 6.7 Hz, 1 H, CHCH3), 7.40–7.50 (m, 2 H,
C7H5), 7.65–7.75 (m, 2 H, C7H5), 7.85–7.95 (m, 1 H, C7H5) ppm.
13
C{1H} NMR (75 MHz, CDCl3): δ = 21.54 (CHCH3), 51.20
(CHCH3), 124.33 (C-7), 128.25 (C-3), 133.40 (C-5), 140.69 and
142.56 (C-4, C-6), 150.00 (C-2), 158.13 (C-8) ppm. MS (EI): m/z
(%) = 272 (100) [M – Cl]+.
Method 2. By Nucleophilic Substitution Reaction Using an Amino-
lithiated Derivative: A 1.6 m solution of nBuLi in hexanes
(0.85 mmol) was slowly added at 0 °C to a solution of 2-(isopro-
pylamino)tropone (0.20 g, 1.23 mmol) in diethyl ether (15 mL). The
yellow solution was warmed to room temperature, stirred for
30 min, and slowly added to a diethyl ether (5 mL) solution of
AsCl3 (0.22 g, 1.23 mmol) at –75 °C. The reaction mixture was
warmed to room temperature and stirred for 3 h. After filtration,
the remaining solid was washed with diethyl ether (3 ⫻ 10 mL). The
volatiles were removed under reduced pressure to yield a yellow
powder. 1H NMR analysis showed the formation of 3 (50 %) and
the presence of the starting ligand, 2-(isopropylamino)tropone
(50 %).
Arsenium Cation 4: Me3SiOTf (0.13 g, 0.59 mmol) was added drop-
wise to a solution of 2 (0.20 g, 0.57 mmol) in CH2Cl2 (5 mL) over
a period of 5 min. The orange solution was stirred for 30 min. After
evaporation of the solvent under reduced pressure, the precipitate
was dissolved in CH2Cl2 and cooled for 24 h at –30 °C. Compound
4 was then isolated as yellow crystals (0.15 g, 59 %). M.p. 160–
163 °C. 19F{1H} NMR (282 MHz, CDCl3): δ = –78.44 ppm. 1H
NMR (300 MHz, CDCl3): δ = 1.58 (d, 3JH,H = 6.4 Hz, 6 H,
CHCH3), 1.81 (d, 3JH,H = 6.4 Hz, 6 H, CHCH3), 4.55 (sept., 3JH,H
= 6.5 Hz, 2 H, CHCH3), 7.56 (t, 3JH,H = 9.5 Hz, 1 H, 5-H), 7.63
(d, 3JH,H = 11.1 Hz, 2 H, 3-H, 7-H), 7.95 (pseudo-t, 3JH,H = 9.6 Hz,
2 H, 4-H, 6-H) ppm. 13C{1H} NMR (75 MHz, CDCl3): δ = 20.81
(CHCH3), 51.16 (CHCH3), 118.40 (q, JCF = 317.4 Hz, CF3), 124.46
(C-3, C-7), 134.08 (C-5), 141.52 (C-4, C-6), 157.95 (C-2, C-8) ppm.
MS (EI): m/z (%) = 427 (22) [M – Cl]+, 313 (100) [M – OSO2-
CF3]+. C14H19AsClF3N2O3S (462.74): calcd. C 36.33, H 4.14, N
6.06; found C 35.92, H 3.91, N 5.90.
3362 www.eurjic.org © 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
L.-C. Pop, A. Castel, L. Silaghi-Dumitrescu, N. Saffon
Reaction of 1a with 3,5-Di-tert-butyl-1,2-benzoquinone: A solution
of 3,5-di-tert-butyl-1,2-benzoquinone (0.13 g, 0.6 mmol) in CH2Cl2
(2 mL) was added to a solution of 1a (0.20 g, 0.7 mmol) in CH2Cl2
(4 mL). The mixture was stirred for 1 h at room temperature and
then heated at 40 °C for 1 h. The mixture was kept at –30 °C for
12 h and then the resulting yellow powder was filtered and dried
under vacuum to give compound 5 (0.24 g, 77 %). M.p. 176 °C.
31
P{1H} NMR (121 MHz, CDCl3): δ = 7.83 ppm. 1H NMR
(300 MHz, CDCl3): δ = 1.22 [s, 9 H, C(CH3)3], 1.31 [s, 9 H,
C(CH3)3], 1.51 (d, 3JH,H = 6.5 Hz, 6 H, CHCH3), 1.54 (d, 3JH,H =
6.7 Hz, 6 H, CHCH3), 4.63 (sept., 3JH,H = 6.7 Hz, 2 H, CHCH3),
7.04 (d, 4JH,H = 2.2 Hz, 1 H, C6H2), 7.47 (d, 4JH,H = 2.2 Hz, 1 H,
C6H2), 7.78 (t, 3JH,H = 9.4 Hz, 1 H, C7H5), 8.16–8.30 (m, 4 H,
C7H5) ppm. 13C{1H} NMR (75 MHz, CDCl3): δ = 19.82 (d, 3JC,P
= 1.5 Hz, CHCH3), 21.21 (CHCH3), 29.50 and 31.55 (C-CH3),
34.49 and 35.41 (C-CH3), 50.19 (d, 2JC,P = 3.3 Hz, CHCH3), 113.63
and 120.17 (C6H2, CH), 124.89 (d, 3JC,P = 10.6 Hz, C-3, C-7),
135.62 (C-5), 137.95 and 141.05 (Cquat of C6H2), 139.61 (d, 2JC,P =
8.0 Hz) and 143.64 (d, 2JC,P = 8.7 Hz, Cquat of C6H2), 144.31 (C-
4, C-6), 151.24 (d, 2JC,P = 18.0 Hz, C-2, C-8) ppm. MS (CI/NH3):
m/z (%) = 490 (14) [M – Cl + H]+. C27H39Cl2N2O2P (524.21): calcd.
C 61.71, H 7.48, N 5.33; found C 60.94, H 7.90, N 5.88.
Presumably due to the adventitious presence of water in the reac-
tion mixture, a very slow recrystallization at –30 °C from CH2Cl2
gave product 6 (0.06 g, 18 %). M.p. 140–142 °C. 31P{1H} NMR
(121 MHz, CDCl3): δ = –3.33 ppm. 1H NMR (300 MHz, CDCl3):
δ = 1.13 [s, 9 H, C(CH3)3], 1.28 [s, 9 H, C(CH3)3], 1.48 (d, 3JH,H =
6.4 Hz, 12 H, CHCH3), 3.89–4.00 (m, 2 H, CHCH3), 6.81–7.05 (m,
5 H, C6H2 and C7H5), 7.37–7.44 (m, 2 H, C7H5) ppm. 13C{1H}
NMR (75 MHz, CDCl3): δ = 20.35 (CHCH3), 28.55 and 30.51 (C-
CH3), 33.25 and 34.11 (C-CH3), 46.82 (CHCH3), 115.19 and 124.27
(CH of C6H2), 125.04 (C-5), 127.20 and 128.00 (C-3, C-7), 135.70
and 140.28 (Cquat of C6H2), 136.81 and 142.77 (Cquat of C6H2),
138.74 (C-4, C-6), 149.58 (C-2, C-8) ppm. MS (EI): m/z (%) = 506
(3) [M – 1]+.
Reaction of 1a with [W(CO)5THF]: A solution of [W(CO)5THF]
(0.44 g, 1.10 mmol), freshly prepared by the irradiation of
[W(CO)6] in THF (20 mL), was added to a stirred suspension of 1
(0.31 g, 1.00 mmol) in THF (6 mL). The reaction mixture was
stirred for 6 h at room temperature and then the solvent was re-
moved from the solution leaving an orange-brown powder. All
attempts to isolate the chloro complex from the crude reaction mix-
ture caused its progressive transformation into 7. A very slow
recrystallization at room temperature from CDCl3 gave crystals of
7 (0.10 g, 16 %). 31P{1H} NMR (121 MHz, CDCl3): δ = 128.65
(JWP = 386 Hz) ppm. 1H NMR (300 MHz, CDCl3, 25 °C): δ = 1.74
(d, 3JH,H = 7.0 Hz, 6 H, CHCH3), 1.84 (d, 3JH,H = 7.1 Hz, 6 H,
CHCH3), 4.72–4.90 (m, 2 H, CHCH3), 7.50–7.60 (m, 1 H), 7.68–
7.95 (m, 4 H) ppm. 13C{1H} NMR (75 MHz, CDCl3): δ = 20.63
(d, 3JC,P = 3.7 Hz, CHCH3), 49.05 (d, 2JC,P = 13.2 Hz, CHCH3),
122.43 (d, 3JC,P = 4.7 Hz, C-3, C-7), 133.22 (C-5), 143.37 (C-4, C-
6), 154.06 (C-2, C-8), 195.20 (d, 2JC,P = 9.3 Hz, COeq), 196.18 (d,
2
JC,P = 8.6 Hz, COax) ppm. IR: ν̃(CO) = 1833, 1904, 2017 cm–1.
X-ray Structural Determination: Structural data were collected with
a Bruker-AXS SMART APEX II diffractometer with Mo-Kα radia-
tion (λ = 0.71073 Å) at low temperatures (173 K for 6, 193 K for
2, 3, 4 and 7) using an oil-coated shock-cooled crystal. The struc-
tures were solved by direct methods[31] and all non-hydrogen atoms
were refined anisotropically by using the least-squares method on
F2.[32]
2: C13H21AsCl2N2O, M = 367.14, monoclinic P21/c, a =
11.6250(13), b = 14.7685(18), c = 9.4324(10) Å, β = 98.6776(6)°, V
Eur. J. Inorg. Chem. 2011, 3357–3364
Aminotroponiminate and Aminotroponate Complexes
= 1600.9(3) Å3, Z = 4, 20953 reflections (4796 independent, Rint
= 0.0309) were collected. Largest diff. peak and hole: 0.339 and
–0.277 e Å–3, R1 [for I ⬎ 2σ(I)] = 0.0252 and wR2 (all data) = 0.0584.
3: C10H12AsCl2NO, M = 308.03, triclinic P1̄, a = 9.6348(2), b =
11.0251(2), c = 13.3230(2) Å, α = 98.4130(10), β = 100.5440(10), γ
= 113.0890(10)°, V = 1242.12(4) Å3, Z = 4, 19949 reflections (6121
independent, Rint = 0.0418) were collected. Largest diff. peak and
hole: 0.474 and –0.502 e Å–3, R1 [for I ⬎ 2σ(I)] = 0.0314 and wR2
(all data) = 0.0692.
4: C14H19AsClF3N2O3S, M = 462.74, monoclinic P21/n, a =
11.5208(6), b = 8.7814(4), c = 19.0636(9) Å, β = 95.613(3)°, V =
1919.39(16) Å3, Z = 4, 5938 reflections [4763 independent, R(int)
= 0.0590] were collected. Largest diff. peak and hole: 0.604 and
–0.560 e Å–3, R1 [for I ⬎ 2σ(I)] = 0.0531 and wR2 (all data) = 0.1488.
6: C29H44Cl5N2O3P, M = 676.88, triclinic P1̄, a = 10.0784(15), b =
10.7719(17), c = 17.733(3) Å, α = 73.226(3), β = 78.009(3), γ =
70.202(3)°, V = 1721.3(5) Å3, Z = 2, 10459 reflections [4832 inde-
pendent, R(int) = 0.1278] were collected. Largest diff. peak and
hole: 0.233 and –0.210 e Å–3, R1 [for I ⬎ 2σ(I)] = 0.0461 and wR2
(all data) = 0.0904.
7: C18H20ClN2O6PW, M = 610.63, orthorhombic Pbca, a =
9.5289(2), b = 13.1917(2), c = 35.3309(6) Å, V = 4441.18(14) Å3, Z
= 8, 75313 reflections [5470 independent, R(int) = 0.0557] were
collected. Largest diff. peak and hole: 0.969 and –1.617 e Å–3, R1
[for I ⬎ 2σ(I)] = 0.0325and wR2 (all data) = 0.0648.
CCDC-811691 (for 2), -811692 (for 3), -811693 (for 4), -811694 (for
6) and -81695 (for 7) contain the supplementary crystallographic
data for this paper. These data can be obtained free of charge
from The Cambridge Crystallographic Data Centre at
www.ccdc.cam.ac.uk/data_request/cif.
Acknowledgments
We thank the ECONET Program (no. 18824SD). L.-C. P. is grate-
ful to The French Ministry of Foreign and European Affairs for
an Eiffel Excellence Scholarship (no. 625658J) and the Romanian
Ministry of Education Research, Youth and Sports (grant no. PN-
II-ID-564).
[1] a) P. W. Roesky, Chem. Soc. Rev. 2000, 29, 335–345; b) H. V. R.
Dias, Z. Wang, W. Jin, Coord. Chem. Rev. 1998, 176, 67–86.
[2] a) D. Pappalardo, M. Mazzeo, P. Montefusco, C. Tedesco, C.
Pellecchia, Eur. J. Inorg. Chem. 2004, 1292–1298; b) S. Dehnen,
M. R. Bürgstein, P. W. Roesky, J. Chem. Soc., Dalton Trans.
1998, 2425–2430; c) F. A. Hicks, M. Brookhart, Organometal-
lics 2001, 20, 3217–3219; d) N. Meyer, K. Löhnwitz, A. Zulys,
P. W. Roesky, M. Dochnahl, S. Blechert, Organometallics 2006,
25, 3730–3734; e) S. Datta, P. W. Roesky, S. Blechert, Organo-
metallics 2007, 26, 4392–4394; f) N. Meyer, R. Rüttinger, P. W.
Roesky, Eur. J. Inorg. Chem. 2008, 1830–1833.
[3] a) M. Sanchez, M. R. Mazières, L. Lamandé, R. Wolf, Phos-
phorous Chemistry, Thieme, Stuttgart, 1990, p. 129; b) D. Gu-
dat, Coord. Chem. Rev. 1997, 163, 71–106.
[4] a) C. J. Carmalt, V. Lomeli, B. G. McBurnett, A. H. Cowley,
Chem. Commun. 1997, 2095–2096; b) G. Reeske, C. R. Hoberg,
N. J. Hill, A. H. Cowley, J. Am. Chem. Soc. 2006, 128, 2800–
2801; c) H. A. Spinney, I. Korobkov, G. A. DiLabio, G. P. A.
Yap, D. S. Richeson, Organometallics 2007, 26, 4972–4982.
[5] a) N. Burford, T. M. Parks, B. W. Royan, B. Borecka, T. S.
Cameron, J. F. Richardson, E. J. Gabe, R. Hynes, J. Am. Chem.
Soc. 1992, 114, 8147–8153; b) T. Gans-Eichler, D. Gudat, M.
Nieger, Heteroat. Chem. 2005, 16, 327–338.
Eur. J. Inorg. Chem. 2011, 3357–3364 © 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
[6] D. Gudat, T. Gans-Eichler, M. Nieger, Chem. Commun. 2004,
2434–2435.
[7] D. Vidovic, Z. Lu, G. Reeske, J. A. Moore, A. H. Cowley,
Chem. Commun. 2006, 3501–3503.
[8] a) T. Kaukorat, I. Neda, R. Schmutzler, Coord. Chem. Rev.
1994, 137, 53–107; b) P. Kilian, A. M. Z. Slawin, Dalton Trans.
2007, 3289–3296; c) S. P. Green, C. Jones, G. Jin, A. Stasch,
Inorg. Chem. 2007, 46, 8–10; d) B. Lyhs, S. Schulz, U. Westphal,
D. Bläser, R. Boese, M. Bolte, Eur. J. Inorg. Chem. 2009, 2247–
2253.
[9] a) C. W. Schultz, R. W. Parry, Inorg. Chem. 1976, 15, 3046–
3050; b) M. G. Thomas, C. W. Schultz, R. W. Parry, Inorg.
Chem. 1977, 16, 994–1001; c) N. Burford, T. S. Cameron, D. J.
LeBlanc, P. Losier, S. Sereda, G. Wu, Organometallics 1997, 16,
4712–4717; d) N. Burford, T. S. Cameron, P. J. Ragona, J. Am.
Chem. Soc. 2001, 123, 7947–7948; e) A. Karaçar, M. Freytag,
H. Thönnessen, P. G. Jones, R. Bartsch, R. Schmultzler, J. Or-
ganomet. Chem. 2002, 643–644, 68–80; f) N. Burford, P. J. Ra-
gona, R. McDonald, M. J. Ferguson, J. Am. Chem. Soc. 2003,
125, 14404–14410.
[10] a) K. A. Porter, A. C. Willis, J. Zank, S. B. Wild, Inorg. Chem.
2002, 41, 6380–6386; b) N. L. Kilah, S. Petrie, R. Stranger, J. W.
Wielandt, A. C. Willis, S. B. Wild, Organometallics 2007, 26,
6106–6113; c) N. L. Kilah, M. L. Weir, S. B. Wild, Dalton
Trans. 2008, 2480–2486.
[11] L.-C. Pop, N. Katir, A. Castel, L. Silaghi-Dumitrescu, F.
Delpech, I. Silaghi-Dumitrescu, H. Gornitzka, D. MacLeod-
Carey, N. Saffon, J. Organomet. Chem. 2009, 694, 1562–1566.
[12] W. Czado, S. Rabe, U. Mueller, Z. Naturforsch. B: Chem. Sci.
1999, 54, 288–290.
[13] N. Burford, T. M. Parks, B. W. Royan, J. F. Richardson, P. S.
White, Can. J. Chem. 1992, 70, 703–709.
[14] a) M. Veith, B. Bertsch, Z. Anorg. Allg. Chem. 1988, 7, 557;
b) D. J. Willliams, M. G. Newton, K. J. Wynne, Cryst. Struct.
Commun. 1977, 6, 167–170.
[15] a) J. Kopf, K. Von Deuten, G. Klar, Inorg. Chim. Acta 1980,
38, 67–69; b) A. L. Rheingold, A.-J. DiMalo, Organometallics
1986, 5, 393–394.
[16] a) C. A. Caputo, J. T. Price, M. C. Jennings, R. McDonald,
N. D. Jones, Dalton Trans. 2008, 3461–3469; b) C. K. SooHoo,
S. G. Baxter, J. Am. Chem. Soc. 1983, 105, 7443–7444.
[17] A. Bond, M. Green, S. C. Pearson, J. Chem. Soc. B 1968, 929–
931.
[18] F. Ramirez, M. Nowakowski, J. F. Marecek, J. Am. Chem. Soc.
1977, 99, 4515–4517.
[19] L. Pauling, Nature of the Chemical Bond, Cornell University
Press, Ithaca, NY, 1960.
[20] L.-C. Pop, D. MacLeod Carey, A. Munoz-Castro, L. Silaghi-
Dumitrescu, A. Castel, R. Arratia-Perez, Polyhedron 2011, 30,
841–845.
[21] D. Gudat, M. Nieger, E. Niecke, J. Chem. Soc., Dalton Trans.
1989, 693–700.
[22] E. Gross, K. Jörg, K. Fiederling, A. Göttlein, W. Malish, R.
Boese, Angew. Chem. Int. Ed. Engl. 1984, 23, 738–739.
[23] a) M. S. Davies, R. K. Pierens, M. J. Aroney, J. Organomet.
Chem. 1993, 458, 141–146; b) G. M. Bodner, Inorg. Chem.
1975, 14, 2694–2699; c) W. Buchner, W. A. Schenk, Inorg.
Chem. 1984, 23, 132–137; d) G. G. Mather, A. Pidcock, J.
Chem. Soc. A 1970, 1226–1229.
[24] a) M. J. Pilkington, A. M. Z. Slawin, D. J. Williams, J. D. Wool-
ins, Main Group Chem. 1995, 1, 145–151; b) Z. Lu, M. Find-
later, A. H. Cowley, Chem. Commun. 2008, 184–186.
[25] M. S. Davies, M. J. Aroney, I. E. Buys, T. W. Hambley, J. L.
Calvert, Inorg. Chem. 1995, 34, 330–336.
[26] M. Alonso, M. A. Alvarez, M. E. Garcia, D. Garcia-Vivo,
M. A. Ruiz, Inorg. Chem. 2010, 49, 8962–8976.
[27] D. E. C. Corbridge in Phosphorus: An Outline of its Chemistry,
Biochemistry and Uses, 5th ed., Elsevier Science, Amsterdam,
1995, p. 336.
www.eurjic.org 3363

FULL PAPER
[28] a) B. Hoge, S. Neufeind, S. Hettel, W. Wiebe, C. Thösen, J.
Organomet. Chem. 2005, 690, 2382–2387; b) B. Hoge, P. Garcia,
H. Willner, H. Oberhammer, Chem. Eur. J. 2006, 12, 3567–
3574.
[29] a) J. Chatt, B. T. Heaton, J. Chem. Soc. A 1968, 2745–2757; b)
C. S. Kraihanzel, C. M. Bartish, J. Am. Chem. Soc. 1972, 94,
3572–3575; c) E. Lindner, B. Schilling, Chem. Ber. 1977, 110,
3266–3271.
3364 www.eurjic.org © 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
L.-C. Pop, A. Castel, L. Silaghi-Dumitrescu, N. Saffon
[30] H. V. R. Dias, W. Jin, R. E. Ratcliff, Inorg. Chem. 1995, 34,
6100–6105.
[31] G. M. Sheldrick, Acta Crystallogr., Sect. A 1990, 46, 467–473.
[32] G. M. Sheldrick, SHELXL-97, Program for Crystal Structure
Refinement, University of Göttingen, Göttingen, 1997.
Received: February 7, 2011
Published Online: June 28, 2011
Eur. J. Inorg. Chem. 2011, 3357–3364