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Encyclopedia of Inorganic and Bioinorganic Chemistry

Chapter · December 2012

DOI: 10.1002/9781119951438.eibc2034

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The Rare Earth Elements: Fundamentals and Applications eibc2034

Tetravalent Chemistry: Organometallic

Farid M. A. Sroor and Frank T. Edelmann*

Chemisches Institut der Otto-von-Guericke-Universität Magdeburg,
Universitätsplatz 2, 39106 Magdeburg, Germany

Abstract
This chapter covers the chemistry of organocerium(IV) complexes as well as "pseudo-
organometallics" of tetravalent cerium. The latter comprise mainly the alkoxides and siloxides as well
as various amido and amidinato complexes of cerium in the oxidation state +4. True
organocerium(IV) complexes are thus far restricted to a handful of cyclopentadienyl derivatives and
some cerocene sandwich complexes. Cerium(IV) complexes comprising specially designed N-
heterocyclic ligands comprise the latest addition to the field.

Keywords
Cerium; Alkoxides; Siloxides; Amides; Amidinates; Cyclopentadienyl complexes; Carbene complexes;
Cyclooctatetraenyl complexes

1. Introduction
Organometallic chemistry of the lanthanide elements in the oxidation state +4 basically means
organocerium(IV) chemistry, as no organometallic compounds have ever been synthesized for other
Ln4+ ions. Among the tetravalent rare earth metal ions, only Ce4+ is readily available in aqueous
solution (E Ce3+/Ce4+ = +1.44 V in 2M H2SO4, 1.61 V in 1M HNO3, 1.70 V in 1M HClO4). The different
values for the reported reduction potentials indicate that stable complexes are formed in these acidic
media. Thermodynamically, oxidation of water by the hydrated Ce4+ ion should be possible, but the
system is kinetically stable. In contrast, the much more positive normal potentials of the other
tetravalent lanthanide ions Pr4+, Nd4+, Tb4+, and Dy4+ (e.g. Pr: +2.86 V) make them very strong
oxidizing agents which readily decompose water under evolution of O2. This is the main reason why
no organometallic compounds have ever been reported for lanthanide(IV) ions other than Ce4+. In this
chapter we will discuss not only "real" organocerium(IV) compounds, i.e. those containing direct Ce-C
bonds, but also several classes of "pseudo-organometallics" which resemble true organolanthanide
complexes in their solubility in organic solvents and/or enhanced volatility. In particular, these include
the alkoxides, siloxides, amides and amidinates of tetravalent cerium. Thus organocerium(IV)
complexes can be divided into three classes, of compounds, i.e. cyclopentadienyl complexes,
 2

complexes containing N-heterocyclic carbene ligands, and cerocenes, i.e. bis(cyclooctatetraenyl)

sandwich complexes.

2. Alkoxides
Tetraalkoxides of cerium form a long known and well established class of lanthanide(IV)
compounds which can be condsidered as "pseudo-organometallic".The effect of difference in both size
and charge should favor the formation of monomeric Ce(IV) alkoxides rather than their trivalent
analogues. Ce4+ is smaller than Ce3+ (0.87 Å vs. 1.01 Å effective ionic radii for 6-coordination
according to Shannon1) and can accommodate four alkoxide ligands as counter ions. Additionally,
"hard" ligands like the alkoxide ligands should stabilize the high oxidation state Ce4+. Lanthanide
alkoxides have been widely used as molecular precursors in materials science. Although Ce(IV)
alkoxides have been known for many years, their preparation was often laborious and time
consuming,2 until the readily available and inexpensive tetravalent cerium reagent ceric ammonium
nitrate (NH4)2[Ce(NO3)6] (= CAN), was utilized for their synthesis. Scheme 1 illustrates how CAN can
be successfully employed as starting material for the preparation of homoleptic cerium(IV) alkoxides.3

(NH4)2Ce(NO3)6 + 4 ROH + 6 NaOMe Ce(OR)4 + 2 NH3 + 6 NaNO3 + 6 MeOH

Scheme 1

Not only can the homoleptic tetraalkoxides be made using this synthetic approach but also a
range of Ce4+ nitrate, mixed nitrate-alkoxide, and alkoxide complexes have become available by
careful control of the reaction stoichiometry. Scheme 2 illustrates this approach. The low costs of the
starting materials and control of the functionalities present rendered this method an appealing route
into further Ce4+ chemistry.3

(NH4)2[Ce(NO3)6] + n NaOtBu

THF
(tBuO)n-2Ce(NO3)6-n(THF)2 + 2 NH3 + n NaNO3 + 2 HOtBu
n = 2-6
Scheme 2

Another access to cerium(IV) tetraalkoxides involves treatment of the readily available

hexachlorocerate(IV) precursor with 4 equivalents of an appropriate alcohol followed by reaction with
ammonia (Scheme 3).2

(pyH)2[CeCl6] + 4 ROH + 6 NH3 Ce(OR)4 + 2 py + 6 NH4Cl

Scheme 3
 3

There is also one interesting report about Ce4+ alkoxides being formed via controlled oxidation
reaction of cerium(III) alkoxide precursors, e.g. by reactions of cerium(III) tris[tri(tert-
butyl)methoxide] with either an organic peroxide or benzoquinone. For example, treatment of
Ce(OCtBu3)3 with dibenzoylperoxide according to Scheme 4 afforded a mixed cerium(IV) alkoxide
carboxylate, which was, however, stable only in solution and decomposed to cerium(III) species when
the reaction was carried out on a preparative scale.4

C 6D 6
2 Ce(OCtBu3)3 + PhC(O)OOC(O)Ph 2 Ce(OCtBu3)3[O C(O)Ph]
25 °C
Scheme 4

Inherent instability was also observed for the mixed alkoxide derivative Ce(OCtBu3)2(OtBu)2
which could be generated by treatment of Ce(OCtBu3)3 with 2 equivalent of di-tert-butyl peroxide
(Scheme 5). The mixed cerium(IV) alkoxide decomposed on attempted isolation under formation of
the dimeric cerium(III) alkoxide product [Ce(OCtBu3)2(OtBu)]2, highlighting the potential instability of
the Ce4+ state in these cases.4

C 6H 6
Ce(OCtBu3)3 + 2 tBuOOtBu Ce(OCtBu3)2(OtBu)2 + [t Bu3COOCtBu3]
Scheme 5

The titration of Ce(OCtBu3)3 with benzoquinone was the cleanest and most easily
characterized oxidation of any in this study. The stoichiometry and NMR spectra were consistent with
formation of a binuclear complex bridged by a hydroquinonediolate as shown in Scheme 6. The
resultant complex was somewhat less soluble than the starting alkoxide and precipitated from solution
as single, well-formed, medium-brown plates suitable for X-ray diffraction. The crystals, once isolated,
gave back purple solutions in C6D6 that yielded the same NMR data as seen in the titration.4

2 Ce(OCtBu3)3 + O C 6D 6 (tBu3CO)3Ce-O O-Ce(OCtBu3)3

O

Scheme 6

Simple homoleptic cerium(IV) tetraalkoxides normally comprise oligomeric structures in the

solid state. Lower aggregates are formed upon adduct formation with O-donor ligands.2 For example,
the tetra(isopropoxide) forms a dinuclear adduct with propan-2-ol. In the dimer Ce2(OiPr)8(HOiPr2)2
each cerium is octahedrally coordinated. Thermolysis of Ce2(OiPr)8(HOiPr2)2 afforded the tetranuclear
oxo-cluster Ce4(µ4-O)(µ3-OiPr2)2(µ-OiPr)8(OiPr3)14. Due to their oligomeric structures, most of the
homoleptic cerium(IV) tetraalkoxides are non-volatile and do not sublime without decomposition. A
notable exception is the tetra-isopropoxide, which can be sublimed under vacuum at ca. 200 °C. The
 4

cerium(IV) alkoxide complex Ce(OCMe2iPr)4, a volatile, non-fluorinated source of cerium, was used as
a chemical vapor deposition (CVD) precursor to cerium oxide films. This complex was prepared
according to Scheme 7 and isolated as a yellow liquid on a multigram scale in 50-60% yield after
vacuum distillation.5

(NH4)2[Ce(NO3)6] + 6 NaOCMe2iPr

Ce(OCMe2iPr)4 + 6 NaNO3 + 2 NH3 + 2 HOCMe2iPr

Scheme 7

A conventional thermal chemical vapor deposition process deposited cerium(IV) oxide films
from Ce(OCMe2iPr)4 on silicon, glass, quartz, lanthanum aluminum oxide (001), and nickel (001)
substrates at low substrate temperatures (<550 °C). The films were highly oriented when the
depositions were carried out on lanthanum aluminum oxide and textured nickel substrates. An X-ray
crystallographic study of Ce(OCMe2iPr)4, which melts at just below room temperature, shows that it is
a loosely bound dimer in the solid state with five-coordinate cerium centers and two bridging alkoxide
ligands. The synthesis and X-ray crystal structures of Ce(OCMe2iPr)4(DMAP)2 (DMAP = 4-
(dimethylamino)pyridine) and Ce2(OCMe2iPr)5(acac)3 have also been reported (Scheme 8). The cerium
atoms in Ce(OCMe2iPr)4(DMAP)2 and Ce2(OCMe2iPr)5(acac)3 have, respectively, distorted octahedral
and pentagonal bipyramidal coordination geometries.5

Ce(OCMe2iPr)4 + 2 DMAP Ce(OCMe2iPr)4(DMAP)2

DMAP = 4-(dimethylamino)pyridine

2 Ce(OCMe2iPr)4 + 3 Hacac i
Ce2(CCMe2 Pr2)5(acac)3 + 3 HOMe2iPr

Scheme 8

The same synthetic route starting with CAN as precursor has been employed for the
preparation of the first homoleptic triorganosiloxides of tetravalent cerium. The reaction shown in
Scheme 9 proceeded in the way that gas (NH3) evolved, a white precipitate (NaNO3) formed, and the
product was isolated in about 70% yield as a light yellow powder. The reaction was carried out in
DME to facilitate isolation of the product as the DME adduct, Ce(OSiPh3)4(DME), and the product was
identical with the crystallographically characterized product isolated by reaction of Ph3SiOH with
Ce(OiPr)4.6
 5

(NH4)2[Ce(NO3)6] + 6 NaOSiPh3

DME
Ce(OSiPh3)4(DME) + 6 NaNO3 + 2 NH3 + 2 Ph3SiOH
Scheme 9

The same preparative route also allowed the synthesis of the corresponding cerium(IV)
tetrakis(triethylsiloxide) (Scheme 10). This compound was isolated as a yellow-brown powder in 83%
yield.6

(NH4)2[Ce(NO3)6] + 6 NaOSiEt3

CH3CN
Ce(OSiEt3)4 + 6 NaNO3 + 2 NH3 + 2 Et3SiOH
Scheme 10

Quite in contrast to the alkoxides and simple siloxides, related disiloxanediolate complexes of
cerium(IV) form spontaneously upon treatment of cerium(III) precursors with 1,1,3,3-tetraphenyl
disiloxanediol (Scheme 11). As a suitable cerium(IV) precursor, the readily available alkoxide nitrate
complex (tBuO)3Ce(NO3)(THF)2 was chosen and treated with (Ph2SiOK)2O (made in situ by
deprotonation of 1,1,3,3-tetraphenyl-1,3-disiloxanediol with KN(SiMe3)2) in a molar ratio of 1:2
according to Scheme 11 (right). From this reaction, the novel heterobimetallic potassium/cerium(IV)
disiloxanediolate complex [{(Ph2SiO)2O}{K(THF)2}]2Ce(OtBu)2 was isolated in the form of yellow,
block-shaped crystals in 81% yield. Its structure was studied by single-crystal X-ray diffraction.7
The same reaction carried out in a molar ratio of 1:3 took a completely different course
(Scheme 11, left). In this case, a light yellow compound could be isolated in high yield (70%), which
was shown by X-ray crystallography to be the novel heterobinuclear potassium/cerium(IV)
disiloxanediolate cluster [{(Ph2SiO)2O}2{(DME)KOtBu}{(Ph2SiO2)K}Ce]2. The X-ray study revealed that
in this compound not only the expected dianions of 1,1,3,3-tetraphenyl-1,3-disiloxanediol act as
ligands but also the dianions of diphenyl-1,1-silanediol, which originate from cleavage of the
disiloxanediolate. Such transformations are not uncommon in the chemistry of silanediolates,
disiloxanediolates, and trisiloxanediolates.7
 6

t
( BuO)3Ce(NO3)(THF)2

3 (Ph2SiOH)2O + 6 KN(SiMe3)2
2 (Ph2SiOH)2O + 4 KN(SiMe3)2

1) THF THF
2) DME

Ph Ph
Si
t Ph O
Bu Ph O Ph2
K t K(THF)2
(DME) K BuO Si Ph Si O
O Si
Ph Ph2
O O Ce O OtBu
O Si O
Ce
O Ce O O Si O t
Ph Ph
2 O Bu
Si O K (DME) O
Ph Si
t
BuO Si O
K t
Bu Ph2 K(THF)2
O Ph Ph
O
Si
Ph Ph

Scheme 11

In a similar manner, the isolation of an unprecedented cerium(IV) silsesquioxane complex

(Scheme 12) has been achieved. Treatment of Ce[N(SiMe3)2]3 with two equivalents of the
incompletely condensed silsesquioxane disilanol derivative Cy8Si8O11(OH)2 in diethyl ether in the
presence of an excess of pyridine exclusively afforded the diamagnetic complex (Cy8Si8O13)2Ce(py)3.
The same compound, albeit in somewhat lower yield, could also be prepared by direct reaction of
anhydrous CeCl3 with two equivalents of Cy8Si8O11(OH)2 in THF/pyridine mixture. Quite surprisingly in
both cases cerium was quantitatively oxidized to the tetravalent oxidation state. An X-ray diffraction
study revealed the presence of the first example of a metallasilsesquioxane derived from the
octameric disilanol ligand [(c-C6H11)8Si8O13]2-. The central Ce atom is coordinated by four oxygen
atoms of two siloxane ligands and three nitrogens of three pyridine molecules resulting in a distorted
pentagonal bipyramidal arrangement.8

Cy Cy Cy Cy
O O
Si Si
Si Si
O Cy py Cy O O O
Cy O O O O Cy
Si O O Si
Cy Si O Si Cy Si Ce Si Cy Si O Si Cy
O O
O O O O
O Si py py Si O
O O
Si Cy Cy Si
Cy O O Cy

Scheme 12
 7

3. Amides
Amido complexes were among the first "pseudo-organometallic" compounds of tetravalent
cerium to be reported in the literature. In the course of the synthesis of the first tri-coordinate
tris(amido)lanthanides in 1972, it had been noted that the yellow Ce[N(SiMe3)2]3 was readily oxidized
by minute traces of air as evident by a formation of a brown material on the surface of the yellow
crystals.9 Ce[N(SiMe3)2]3 was by far the most air-sensitive compound in the entire series of
Ln[N(SiMe3)2]3 derivatives. Thus this compound appeared to be a logical choice as starting material
for the synthesis of cerium(IV) silylamido complexes. However, various oxidizing agents including
elemental chlorine or bromine only led to the formation of decomposition products. The list of other
failed alternative oxidants that have been compiled for this cerium amide is quite lengthy: I2, N-
bromosuccinimide, N-chlorosuccinimide, AgBF4, AgCN, Hg(C6F5)2, PbCl2, and tBuOOtBu were all tried
and in all cases only unreacted Ce[N(SiMe3)2]3 was recovered. Only the use of the uncommon reagent
TeCl4 allowed for the first time the isolation of [(Me3Si)2N]3CeCl. It furnished well-formed purple/black
needles, although the workup procedure had to be carried out rapidly as delays resulted in the
deposition of colorless blocks of [Ce{N(SiMe3)2}2(µ-Cl)(THF)]2 as a by-product in significant amounts.
The analogous bromo- derivative [(Me3Si)2N]3CeBr was made by treatment of the cerium(III)
silylamide with Ph3PBr2 (Scheme 13).10,11

Me3Si
N
SiMe3
Me3Si
Ce N
Me3Si SiMe3
N

1/4 TeCl4 SiMe3

Ph3PBr2
THF or toluene Et2O

Me3Si Cl
Me3Si Br
N SiMe3 N SiMe3
Me3Si
Ce N Me3Si
Ce N
Me3Si SiMe3
N Me3Si SiMe3
N

SiMe3
SiMe3
Scheme 13

Most recently it has been reported that phenyliodine(III) dichloride, PhICl2, can be
successfully employed as an innovative and superior reagent for the one-electron oxidation of
cerium(III) precursors. The hypervalent organoiodine(III) compound PhICl2 has several significant
advantages: (a) it is readily accessible from inexpensive, commercially available starting materials; (b)
 8

solid PhICl2 can easily be employed in exact stoichiometric amounts; and (c) liquid, highly soluble, and
volatile iodobenzene is the only iodine-containing byproduct. All these assumptions could be verified
by a test reaction with the silylamide Ce[N(SiMe3)2]3. Treatment of a toluene solution of
Ce[N(SiMe3)2]3 with the calculated amount of PhICl2 in toluene (Scheme 14) resulted in an immediate
color change from orange to purple. Pure [(Me3Si)2N]3CeCl could be isolated in 10% yield in a very
simple manner by crystallization from the concentrated reaction mixture at -20 °C. The
organoiodine(III) route could be also utilized to access novel five-coordinate cerium(IV) amido
species. Dark red-brown [(Me3Si)2N]3CeCl(NºCC6H4OMe-p) was isolated in 45% yield by adding p-
anisonitrile to a toluene solution of Ce[N(SiMe3)2]3 prior to treatment with PhICl2.12 Trityl chloride,
Ph3CCl, has also been found to be a very convenient reagent for the oxidative halogenation of
cerium(III) amide precursors such as Ce[N(SiMe3)2]3.13

N(SiMe3)2
(Me3Si)2N Ce
N(SiMe3)2
1/2 PhICl2 1. RC N
toluene Cl
- 1/2 PhI
Cl 2. 1/2 PhICl2 N(SiMe3)2
toluene (Me3Si)2N Ce
Ce -1/2 PhI N(SiMe3)2
N(SiMe3)2 N
(Me3Si)2N
N(SiMe3)2
C
R

R = p-MeOC6H4

Scheme 14

Unprecedented crystalline cerium(IV) bis(amides) containing a cyclic (Ce–O)n core (n = 2, 3,

or 4) have been prepared by oxidation of Ce[N(SiMe3)2]3 or Ce(NR”2)3 (NR”2 = NC(Me)2(CH2)3CMe2).
The bis(trimethylsilyl)amides were prepared using oxygen gas or 2,6-di(tert-butyl)-1,4-
benzoquinone/a trace H2O at low temperature as illustrated in Scheme 15. These complexes were
obtained as X-ray quality crystals in modest (38% for the dimer) or low (10% for the trimer) yield, 1H
and 13
C{1H} NMR spectra in C6D6 showed each complex to be diamagnetic. However, the solutions
decomposed after a few hours at ambient temperature.14
 9

Ce(NR2)3
O2 2,6-tBu2-benzoquinone,
R = SiMe3 then traces of H2O
C6H14, -27 °C

O R2N NR2
R2N NR2 O
Ce Ce R2N Ce Ce NR2
R2N NR2
O O O
red Ce

R2N NR2

dark purple
Scheme 15

In a similar manner, oxidation of the tetramethylpiperidide derivative Ce(NR”2)3 (NR”2 =

NC(Me)2(CH2)3CMe2) with elemental oxygen as shown in Scheme 16 produced a tetrameric
bis(amido)cerium(IV) oxide, although only a few single crystals of this compound could be isolated.14

NR''2
NR''2
R''2N Ce
O
R''2N Ce O
O2, PhMe
Ce(NR''2 )3 O Ce NR''2
- 27 °C O
Ce NR''2
R''2N
NR''2

dark purple

NR''2 = NC(Me)2(CH2)3CMe2

Scheme 16

The black binuclear complexes (µ-η2:η2-O2)[Ce{N(SiMe3)2}2]2・2CnH2n+2 (n = 5, 6), obtained in

a similar manner from Ce[N(SiMe3)2]3 and dry oxygen, have either a bridging per- or superoxide
ligand, but the O–O bond length data were not definitive. The preparation of related novel sodium
and potassium bis(trimethylsilyl)amido (oxo)cerates(IV) is outlined in Scheme 17. Each of these
compounds was obtained from a mixture of the cerium(III) amide Ce[N(SiMe3)2]3 and the appropriate
metal amide MN(SiMe3)2 (M = Na, K).14
 10

R2N NR2 R2N NR2

Na K
R2N R2N
Ce O O Ce Ce O O Ce
Na NR2 NR2
R2N R2N K
NR2 NR2
dark brown dark brown

NaNR2, O2, C6H14, - 27 °C KNR2, O2, C6H14, - 27 °C

[Ce(NR2)3]
R = SiMe3

KNR2, O2, H2, C6H14, - 27 °C

NR2
R2N NR2
K O Ce
R2N NR2
R2N Ce O O Ce
K NR2
Ce O
R2N
NR2
R2N
red-brown
Scheme 17
Facile oxidation of Ce(NCy2)3(THF) or Ce(NCy2)2(µ-NCy2)2Li(THF) (Cy = cyclohexyl) with dry
air produced the first homoleptic Ce(IV) amide Ce(NCy2)4 as illustrated in Scheme 18. Both cerium(III)
precursors were extremely air-sensitive in solution and if the smallest amount of air was accidentally
introduced during the work-up, a blue coloration appeared in the solution immediately, later yielding
black microcrystals. When a measured amount of dry air was added to toluene or THF solutions of
Ce(NCy2)3(THF) or Ce(NCy2)2(µ-NCy2)2Li(THF) the diamagnetic Ce(IV) amide Ce(NCy2)4 was isolated in
a moderate yield. Ce(NCy2)4 is only sparingly soluble in hexane, benzene, toluene or THF, producing
deep blue solutions, which could be stored in a vacuum-sealed tube without decomposition for several
months at room temperature (in contrast to the solution instability of Ce[N(SiMe3)2]3X (X = Cl, Br).
The solubility increased upon heating to 70 °C thus allowing recrystallisation of Ce(NCy2)4 without
noticeable decomposition even at this temperature.15

3 LiNCy2 O2
CeCl3(THF)x Ce(NCy2)3(THF) Ce(NCy2)4
THF PhMe

1. THF
4 LiNCy2 2. PhMe / hexane O2
PhMe
Ce(NCy2)2(µ-N Cy2)2Li(THF)
 11

Scheme 18

The synthesis and characterization of the related first neutral cerium dialkyl dithiocarbamate
complexes, using a novel oxidative displacement of the amido ligands of Ce[N(SiMe3)2]3 by
tetraalkylthiuram disulfides [R2NC(S)S]2 (R = Me, Et) in THF solution, has also been reported. The
crystalline, toluene-soluble cerium(IV) dithiocarbamate Ce(κ2-S2CNEt2)4 was made by briefly bubbling
oxygen gas through a suspension of the yellow Ce(κ2-S2CNEt2)3 in toluene at ambient temperature.
The reaction was rapid, as evident from the almost immediate colour change to the black tetravalent
complex.16
Particularly remarkable was the stabilization of cerium(IV) in the presence of an iodide ligand,
as neither CeI4 nor stable salts containing the hexaiodocerate(IV) anion , [CeI6]2-, have ever been
isolated. This was achieved by reaction of triamidoamine complex Ce(NN'3) [NN'3 =
t
N(CH2CH2NSiMe2 Bu)3] with iodine to give (NN'3)CeI. The base-free trivalent precursor complex
Ce(NN'3) was readily synthesized according to Scheme 19 by treatment of CeCl3(THF)4 with
Li3(THF)3(NN'3) in dry THF followed by sublimation in vacuo. This bright yellow-orange complex
decomposes rapidly in air but is otherwise quite stable. The reaction of Ce(NN'3) as a solution in
pentane with 0.5-1.5 equiv of elemental chlorine led to an immediate color change to purple and
deposition of large purple crystals of the fascinating mixed valence Ce3+/4+ complex (µ-Cl)[Ce(NN'3)2].
Similarly, reaction of Ce(NN'3) with bromine gave purple (µ-Cl)[Ce(NN'3)2]. Most unexpectedly,
however, the weakest oxidizing agent iodine gave the purple cerium(IV) iodide complex, (NN'3)CeI
(Scheme 19).17
 12

R
N R
(i) CeCl3(THF)4 Ce N
Li3(NN'3)(THF)3
(ii) sublime N
R
N

R I
I2
N R X2
Ce N

N
R
N
N
R
t
N
R = SiBu Me2
N Ce
R N
R
X

R
N R
Ce N

N
N
R

X = Cl, Br
Scheme 19

4. Amidinates
Amidinate and guanidinate anions are nitrogen analogues of the carboxylates. They have
been widely employed as spectator ligands in main group and transition metal coordination chemistry,
with the latter encompassing both early and late transition metals as well as the lanthanides and
actinides. These chelating anions are generally readily accessible using commercially available or
easily prepared starting materials. Furthermore, their steric and electronic properties can be readily
modified in a wide range through variation of the substituents on the carbon and nitrogen atoms.
These properties combined make the amidinate anions clearly almost as versatile as the ubiquitous
cyclopentadienyl ligands.18
Most recently it was discovered that amidinate ligands are also capable of stabilizing novel
cerium(IV) species. Thus they belong to the limited number of organic ligands which allow the
stabilization of lanthanide complexes in all possible oxidation states (+2, +3, and +4). For example,
treatment of anhydrous cerium(III) trichloride with three equivalents of the lithium amidinate
precursor Li[p-MeOC6H4C(NSiMe3)2] first afforded the bright yellow p-anisonitrile adduct of the
cerium(III) amidinate (Scheme 20). Oxidation to the corresponding cerium(IV) amidinate [p-
MeOC6H4C(NSiMe3)2]3CeCl was readily achieved using the reagent phenyliodine(III) dichloride (vide
supra). This way the almost black cerium(IV) species could be isolated by simple crystallization
 13

directly from the concentrated reaction mixture. A single-crystal X-ray analyses clearly established the
presence of the first amidinate complex of tetravalent cerium.12

OMe
OMe

SiMe3 NC
SiMe3 C N SiMe3
N Me3Si N N
THF
3 Li MeO C + CeCl3 CeIII C OMe
- 3 LiCl
N Me3Si N N
SiMe3 C N SiMe3
SiMe3

MeO

OMe 1/2 PhICl2

toluene - 1/2 PhI

SiMe3
C N Cl SiMe3
Me3Si N N
IV
Ce C OMe
Me3Si N N
C N SiMe3
SiMe3

MeO

Scheme 20

5. Cyclopentadienyl Complexes
For cerium the oxidation state +4 is remarkably stable because Ce4+ has the electronic
configuration of xenon. Thus cerium should be by far the best candidate for making stable
organolanthanide(IV) complexes. Historically, however, this was a notoriously difficult task, and it was
a fundamental question persisting for decades in organolanthanide chemistry whether tetravalent
organocerium complexes would exist at all. It is interesting to note that early reports on the synthesis
of organometallic cerium(IV) complexes published in the 1970's were all found to be irreproducible or
were shown to yield Ce3+ species. In particular, reactions of (pyH)2[CeCl6] with cyclopentadienyl or
indenyl reagents invariably led to reduction processes and formation of Ce3+ products. Even until
today well-characterized organocerium(IV) complexes remain scarce. Early reports19 about the
synthesis of CeCp4 and Ce(C9H7)4 (C9H7 = indenyl) have later been refuted.20 The same is true for
many other compounds of the types Cp3CeX and (C9H7)2CeX2 (X = H, alkyl, aryl, BH4, Cl, NH2, N3, CN,
NCO, NCS, NO2, NO3, SR, and O2CR).
The first well-characterized cyclopentadienyl complexes of tetravalent cerium were the
alkoxide derivatives Cp3Ce(OR) (R = iPr, tBu) and Cp2Ce(OtBu)2. The first compound of this type,
Cp3Ce(OiPr), was obtained in minute quantities (4% yield) upon treatment of cerium(IV) tetra-
 14

isopropoxide with magnesocene according to Scheme 21. The new complex Cp3Ce(OiPr) could be
isolated by sublimation from the reaction mixture in the form of black microcrystals.21

i benzene i i
3 Cp2Mg + 2 Ce(O Pr)4 2 Cp3Ce(O Pr) + 3 Mg(O Pr)2
20 °C
Scheme 21

About ten years later, a more convenient route has been developed which involves treatment
of the same alkoxide precursor with 3 equivalents of Me3SnCp according to Scheme 22.22 This method
uses an organotin compound which is a weaker reducing agent than the alkali or alkaline earth metal
cyclopentadienides, and is thus less likely to result in reduction to Ce3+. With 69% isolated yield the
new synthetic route represented a major improvement over the previously reported synthesis.21 The
product was shown to be a genuine Ce4+ complex by NMR, elemental analysis, and cyclic
voltammetry/controlled potential coulometry in Bu4N+BF4-/THF. The latter data indicated that
Cp3Ce(OiPr) is a relatively strong oxidizing agent (E1/2 = +0.32 vs SSCE) and that one-electron
reduction is both electrochemically and chemically reversible. Eiectronic structure calculations at the
nonrelativistic Xα-DVM level suggested non-negligible Ce-Cp f orbital covalency and yielded transition
state ionization energies in good agreement with He I/He II photoelectron spectra.22

65 °C
Ce(OiPr)4 + 3 R3SnCp Cp3Ce(OiPr) + 3 R3Sn(OiP r)
toluene

R = CH3, 69% yield

R = nBu, 20% yield
Scheme 22

An alternative synthetic route utilizes the readily available mixed-ligand alkoxide/nitrate

complexes3 of tetravalent cerium as starting materials. For example, the dark brown compound
Cp2Ce(OtBu)2 can be prepared in high yield (90%) by treatment of Ce(OtBu)2(NO3)2(THF)2 with 2
equivalents of NaCp as shown in Scheme 23.23

OtBu
Ce(OtBu)2(NO3)2(THF)2 + 2 NaCp Ce + 2 NaNO3
OtBu

Scheme 23
t
It was also found that Ce(O Bu)(NO3)3(THF)2 reacts with 3 equivalents of NaCp to form
Cp3Ce(OtBu) (Scheme 24) admixed with Cp2Ce(OtBu)2 from which it can be separated by
 15

crystallization and isolated in 50% yield as a black microcrystalline powder. The molecular structure of
Cp3Ce(OtBu) was unambiguously verified by X-ray diffraction.23

THF
2 Ce(OtBu)(NO3)3(THF)2 + 6 NaCp Ce + Cp2Ce(OtBu)2 + 6NaNO3
+ other products
OtBu

Scheme 24

Recently, a further example of the versatility of PhICl2 as an oxidant was demonstrated by the
synthesis and structural characterization of tris(cyclopentadienyl) cerium(IV) chloride (Scheme 25),
the long sought-after cerium(IV) analogue of Cp3UCl. A material thought to be Cp3CeCl was first
described in 197119 but that report was later refuted.20 Addition of 0.5 equivalents of PhICl2 to a
toluene solution of Cp3Ce produced an immediate color change from yellow to black. Black crystals
were isolated, after removing the volatiles, from a concentrated toluene solution at –35 °C in 15%
yield. Diamagnetic Cp3CeCl displays a singlet at δ 4.74 in the 1H NMR spectrum in C6D6. X-ray
diffraction analysis revealed these crystals to be Cp3CeCl. Thus Cp3CeCl is not only the first new
tris(cyclopentadienyl)cerium(IV) complex reported in more than 20 years but also the first chloro-
funtional species of this type for which a promising derivative chemistry can be envisioned.12

Ce

Cl
Scheme 25

6. Carbene complexes
An interesting recent addition to organocerium(IV) chemistry is the succssful synthesis and
characterization of Ce4+ complexes containing a bidentate N-heterocyclic carbene alkoxide ligand,
[C{(NiPr)CHCHN}CH2CMe2O]-. Treatment of CeI3(THF)4 with three equivalents of KL, K[OCMe2CH2(1-
C{NCHCHNiPr})], afforded CeL3 in good yield as a dark yellow microcrystalline powder (Scheme 26).
Treatment of CeL3 with TeCl4, PBr2Ph3 or I2 (reagents previously used for the oxidation of Ce3+
amides) did not yield the desired oxidation products. However, treatment of CeL3 with benzoquinone
afforded tetravalent CeL4, arising from oxidation and ligand redistribution (Scheme 26). The oxidation
could also be effected by XeF2 and by [Cp2Fe][OTf], but with lower yields. Subsequent treatment of
CeL4 with 2 equivalents of the borane 9-BBN, 9-borabicyclo[3.3.1]nonane, afforded highly crystalline
yellow L2Ce(L-9BBN)2 (Scheme 26).24
 16

CeI3(THF)4 + 3 KL

THF
-3 KI

O
+
Pri
O N
N O O N
N IV
+ KL
O Ce
N THF O
N
Ce O O
Pri O N Pri
- [K-OArO]n-
Pri N N N
N N N
N Pri Pri Pri

Pri
N + 2 9-BBn
O N
N IV THF
Ce
N O
Pri O O
BH HB
N N
N N Pri
Pri
Scheme 26

More recently it was found that trityl chloride is an excellent reagent to achieve the oxidative
halogenation of cerium(III) carbene precursors. Scheme 27 illustrates a typical reaction.13

O N(SiMe3)2 O N(SiMe3)2
PhMe
Ce + Ph3C-Cl Ce Cl
N N(SiMe3)2 Ph3C N
Ph N(SiMe3)2
N N
Dipp H Ph Dipp
Dipp = 2,6-diisopropylphenyl
Scheme 27

7. Cerocenes
Cerocene, Ce(C8H8)2 (Scheme 28), is a particularly interesting metallocene that is formally a
lanthanide(IV) analogue of uranocene, U(C8H8)2, but combines a strong oxidizing agent, Ce4+, and a
 17

strong reducing agent, cyclooctatetraene (COT) dianion, in the same molecule. The first successful
synthesis of cerocene resulted surprisingly from the use of a reducing agent, triethylaluminum, in a
reaction using cerium(IV) isopropoxide with neutral cyclooctatetraene as a reactant and solvent.
Cerocene was isolated as a black-red, pyrophoric solid.21 A more straightforward synthesis involves
oxidation of the anionic cerium(III) sandwich complex K[Ce(C8H8)2] with AgI. The longer known
anionic derivative K[Ce(C8H8)2] can be regenerated by reduction of cerocene with potassium metal.
Yet another efficiently modified synthesis for unsubstituted cerocene involves oxidation of
K[Ce(C8H8)2] with allyl bromide.25

Ce

Scheme 28

In order to cope with the pyrophoric nature of the parent cerocene, synthetic routes to silyl-
substituted cerocenes have been developed. These cerocene derivatives can be isolated as deep
purple materials which are readily soluble even in non-polar organic solvents. Scheme 29 illustrates a
typical reaction sequence leading to 1,1',4,4'-tetrakis(trimethylsilyl)cerocene.26

SiMe3 Li(thf)n
THF SiMe3
+ 2 BuLi + CeCl3

- 2 BuH - 3 LiCl
SiMe3
SiMe3 Li(thf)n

Me3Si Me3Si

+ Me3Si + Agl (excess) Me3Si

Li Ce Ce
SiMe3 SiMe3
- Ag, Lil

SiMe3 SiMe3

Scheme 29
In this case, silver iodide was found to be the reagent of choice for achieving the oxidation of
the anionic intermediate. 1,1',4,4'-tetrakis(trimethylsilyl)cerocene was isolated as a dark purple oil
which is stable in air for short periods of time. A crystalline poly-substituted cerocene derivative was
 18

synthesized as illustrated in Scheme 30 by employing the newly developed 1,3,6-

tris(trimethylsilyl)cyclooctatetraenyl ligand. The resulting 1,1',3,3',6,6'-hexakis(trimethylsilyl)cerocene
forms dark purple, low-melting crystals.26

Li(thf)n
SiMe3 Me3Si SiMe3
+ 2 Me3SiCl
SiMe3
- 2 LiCl
SiMe3 Me3Si
Li(thf)n

K(thf)n
THF SiMe3
+ 4 KH Me3Si Ce(O3SCF3)3
2
-2 H2, -2 HSiMe3 - 3 KO3SCF3
SiMe3
K(thf)n

SiMe3 SiMe3
Me3Si Me3Si

SiMe3 + Agl (excess) SiMe3

K+ Ce Ce
Me3Si Me3Si
- Ag, -Kl

SiMe3 SiMe3
Me3Si Me3Si

Scheme 30

Subsequent work in this field has provided further characterization of cerocene and various
ring-substituted analogues. Crystal structures of Ce(C8H7Me)227 and Ce[C8H5(SiMe3)3]226 showed that
cerocenes have a uranocene-type sandwich structure with ring centroid-Ce-ring centroid angles of
176° in both cases. In all cases the cyclooctatetraenyl ligands are η8-coordinated to cerium. There is
theoretical and spectroscopic evidence (e.g. self-consistent field calculations) that the ground state in
cerocene is almost entirely 4f1 and that this formally tetravalent cerium sandwich complex is better
described as a cerium(III) compound such as Ce3+[(C8H8)2]3-.28,29
Surprising structural features have recently been discoverd for related cerium sandwich
complexes containing the superbulky 1,4-bis(triphenylsilyl)cyclooctatetraenide ligand (= COTBIG).30
First the anionic cerium(III) sandwich complex [Li(DME)2][Ce(COTBIG)2] was prepared by reaction of
CeCl3 with 2 equivalents of Li2(COTBIG) made in situ in DME (Scheme 31). A single-crystal X-ray
 19

analysis showed that in contrast to all previously reported [Ln(COT)2]- or [Ln(COT'')2]- derivatives the
anion in [Li(DME)2][Ce(COTBIG)2] is significantly bent (tilt angle between the eight membered rings:
15.1°). Knowing the bent structure of the anionic sandwich complex, it was tempting to see if the
bending would increase upon oxidation. AgI oxidation of [Li(DME)2][Ce(COTBIG)2] proceeded smoothly
with formation of the neutral cerocene Ce(COTBIG)2 (Scheme 31, dark purple needles, 63%). X-ray
diffraction analysis of Ce(COTBIG)2 unexpectedly revealed the presence of strictly co-parallel rings, but
the molecule now contains the 1,3-isomer of the COTBIG ligand. Obviously steric pressure becomes too
severe upon oxidation to the neutral cerocene that SiPh3 group migration is induced for relief,
resulting in a sterically more relaxed and highly symmetrical molecular structure of Ce(COTBIG)2 as a
result of this unprecedented rearrangement.30

Ph3Si SiPh3
Ph3Si
SiPh3
SiPh3
1. 2 nBuLi
2. 1/2 CeCl3 AgI (THF)
[Li(DME)2] Ce Ce
(DME) - LiI
- 1.5 LiCl
SiPh3 Ph3Si SiPh3
Ph3Si SiPh3

Scheme 31

8. Conclusions and future outlook

The synthesis and full characterization of organolanthanide(IV) complexes remain a very difficult and
often unpredictable task. Thus far, organolanthanide chemistry in the oxidation state +4 remains
entirely limited to cerium. This can be traced back to the very highly positive normal potentials of the
other tetravalent lanthanide ions Pr4+, Nd4+, Tb4+, and Dy4+ (e.g. Pr: +2.86 V) which make them very
strong oxidizing agents. Not even well-defined "pseudo-organometallics" (i.e. alkoxides, amides and
related compounds) of tetravalent lanthanide ions other than Ce4+ have ever been isolated. Only
alkoxides and amides of tetravalent cerium form fairly well-investigated classes of compounds. In
contrast, true organocerium(IV) containing Ce-C bonds remain scarce. The oldest compounds of this
type are cerocene and its derivatives, although the elctronic structure of these species is far from
being fully understood. The chemistry of cerium(IV) complexes containing N-heterocyclic carbene
ligands is just emerging, and even cyclopentadienyl complexes of the type Cp3CeX (X = Cl, OR) are
limited to a handful of compounds. The recently reported chloro derivative Cp3CeCl12 could turn out to
be the starting point for a more diverse derivative chemistry. The successful synthesis of "non-
classical" organolanthanide(IV) compounds of Pr4+, Nd4+, Tb4+ or Dy4+ would certainly constitute a
major break-through in this area. However, given the current knowledge, the design of suitable
ligands for such highly oxidizing species will be very difficult if not impossible.
 20

9. Glossary
acac Acetylacetonate
9-BBN 9-Borabicyclo[3.3.1]nonane
CAN Ceric ammonium nitrate, (NH4)2[Ce(NO3)6]
Cerocene Bis(η8-cyclooctatetraenyl)cerium
COT Cyclooctatetraene or η8-cyclooctatetraenyl ligand
COT'' 1,4-Bis(trimethylsilyl)cyclooctatetraenyl
COTBIG 1,4-Bis(triphenylsilyl)cyclooctatetraenyl
Cp Cyclopentadienyl anion
CVD Chemical vapor deposition
Cy Cyclohexyl
Dipp 2,6-Diisopropylphenyl
DMAP 4-(Dimethylamino)pyridine
DME 1,2-Dimethoxyethane
E1/2 Half-wave potential
NN'3 N(CH2CH2NSiMe2tBu)3
NR”2 NC(Me)2(CH2)3CMe2
OTf Triflate anion, CF3OSO2-
py Pyridine
SCE Silver / silver chloride-electrode
Uranocene Bis(η8-cyclooctatetraenyl)uranium

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