Chapter 24 .

Organometallic complexes of the lanthanoids

751

APPLICATIONS
Box 24.4 Lanthanoid shift reagents in NMR spectroscopy
The magnetic eld experienced by a proton is very dierent
from that of the applied eld when a paramagnetic metal
centre is present, and results in the  range over which the 1 H
NMR spectroscopic signals appear being larger than in a spectrum of a related diamagnetic complex (see Box 2.5). Signals
for protons close to the paramagnetic metal centre are signicantly shifted and this has the eect of spreading out the spectrum. Values of coupling constants are generally not much
changed.
1
H NMR spectra of large organic compounds or of
mixtures of diastereomers, for example, are often dicult
to interpret and assign due to overlapping of signals. This
is particularly true when the spectrum is recorded on a
loweld (e.g. 100 or 250 MHz) instrument. Paramagnetic
lanthanoid complexes have application as NMR shift
reagents. The addition of a small amount of a shift reagent
to a solution of an organic compound can lead to an equilibrium being established between the free and coordinated
organic species. The result is that signals due to the organic
species which originally overlapped, spread out, and the

Lower coordination numbers can be stabilized by using

aryloxy or amido ligands, for example:
. 5-coordinate: (24.2), (24.3);
. 3-coordinate: NdfNSiMe3 2 g3 .

In the solid state, NdfNSiMe3 2 g3  is trigonal pyramidal

but this may be a consequence of crystal packing forces
(see Section 19.7).

spectrum becomes easier to interpret. The europium(III)

complex shown below is a commercially available shift
reagent (Resolve-AlTM ), used, for example, to resolve
mixtures of diastereomers.
tBu

tBu

Bu
O

O
Eu
O

O
tBu

Bu

Bu

See also: Box 2.6 for application of Gd(III) complexes as

MRI contrast agents.

23.4 and 23.9), lanthanoid metals do not form complexes

with CO under normal conditions. Unstable carbonyls
such as Nd(CO)6 have been prepared by matrix isolation.
Organolanthanoids are usually air- and moisture-sensitive
and some are pyrophoric; handling the compounds under
inert atmospheres is essential.

-Bonded complexes
Reaction 24.16 shows a general method of forming LnC
-bonds.

LnCl3 3LiR  LnR3 3LiCl

"

R2N

Nd

NR2

RO

Sm

NR2
O

OR
OR

24:16

In the presence of excess LiR and with R groups that are

not too sterically demanding, reaction 24.16 may proceed
further to give LnR4  or LnR6 3 (equations 24.17 and
24.18).
THF; 218 K

R = SiHMe2

R = 3,5-iPr2C6H3

(24.2)

(24.3)

YbCl3 4t BuLi  LiTHF3  Ybt Bu4  3LiCl

24:17
"

DME; 195 K

3
3LiCl
LuCl3 6MeLi  LiDME
3 LuMe6 
"

DME=1,2-dimethoxyethane

24.8 Organometallic complexes of the

lanthanoids
Organolanthanoid chemistry is a rapidly expanding research
area, and an exciting aspect of this area is the number of
ecient catalysts for organic transformations that have
been discovered (see Box 24.5). In contrast to the extensive
carbonyl chemistry of the d-block metals (see Sections

24:18

In the solid state, LuMe6 3 is octahedral (LuC 253 pm)

and analogues for all the lanthanoids except Eu are known.
In these reactions, a coordinating solvent such as DME or
Me2 NCH2 CH2 NMe2 (TMED) is needed to stabilize the

For details of inert atmosphere techniques, see: D.F. Shriver and M.A.
Drezdon (1986) The Manipulation of Air-sensitive Compounds, Wiley,
New York.