Lutetium complexes with the 1,3-diphenylcyclopentadienyl ligand. Syntheses and molecular structures of the complexes {(Ph2C5H 3)Lu(C2Ph4)(THF)} and {(Ph2C 5H3)LuCl2(THF)3}

Article abstract of DOI:10.1007/s11172-007-0308-5

The reaction of LuCl₃(THF)₃ with Na(1,3-Ph ₂C₅H₃) followed by the in situ reaction with Na₂[Ph₄C₂] produced (1,3-Ph₂C ₅H₃)Lu(Ph₄C₂)(THF) (1). The structure of 1 was established by X-ray diffraction. In the crystal structure of 1, the bis-allyl η⁶-coordination of the tetraphenylethylene dianion to the lutetium cation was observed. The structures of (1,3-Ph ₂C₅H₃)LuCl₂(THF)₃ and (C₅H₅)LuCl₂(THF)₃ were determined by X-ray diffraction.

Full text of DOI:10.1007/s11172-007-0308-5

Russian Chemical Bulletin, International Edition, Vol. 56, No. 10, pp. 1978—1985, October, 2007
1978
Lutetium complexes with the 1,3ꢀdiphenylcyclopentadienyl ligand.
Syntheses and molecular structures of the complexes
{(Ph2C5H3)Lu(C2Ph4)(THF)} and {(Ph2C5H3)LuCl2(THF)3}
D. M. Roitershtein,a,b M. E. Minyaev,a,b A. A. Mikhailyuk,b K. A. Lyssenko,c P. A. Belyakov,d and M. Yu. Antipinc
ꢀ
aL. Ya. Karpov Institute of Physical Chemistry,
10 ul. Vorontsovo Pole, 105064 Moscow, Russian Federation.
Fax: +7 (495) 975 2450. Eꢀmail: roiter@server.ioc.ac.ru
bDepartment of Chemistry and Biology, Moscow City Pedagogical University,
4 Vtoroi Sel´skokhozyaistvennyi proezd, 129226 Moscow, Russian Federation.
cA. N. Nesmeyanov Institute of Organoelement Com pounds, Russian Academy of Sciences,
28 ul. Vavilova, 119991 Moscow, Russian Federation.
Fax: +7 (499) 135 5085
dN. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences,
47 Leninsky prosp., 119991 Moscow, Russian Federation.
Fax: +7 (499) 135 5328
The reaction of LuCl3(THF)3 with Na(1,3ꢀPh2C5H3) followed by the in situ reaction with
Na2[Ph4C2] produced (1,3ꢀPh2C5H3)Lu(Ph4C2)(THF) (1). The structure of 1 was estabꢀ
6
lished by Xꢀray diffraction. In the crystal structure of 1, the bisꢀallyl η ꢀcoordination of
the tetraphenylethylene dianion to the lutetium cation was observed. The structures of
(1,3ꢀPh2C5H3)LuCl2(THF)3 and (C5H5)LuCl2(THF)3 were determined by Xꢀray diffraction.
Key words: organolanthanide compounds, lutetium, dianion, tetraphenylethylene,
diphenylcyclopentadiene.
In the last 10—15 years, extensive study has been
given to lanthanide complexes with substituted cycloꢀ
pentadienyl ligands, in which both the nature of the ligands
and the degree of substitution in the cyclopentadienyl
ring were varied. However, lanthanide complexes with
phenylꢀsubstituted cyclopentadienyl ligands have reꢀ
ceived little attention. A few complexes with the folꢀ
lowing polyphenylꢀsubstituted cyclopentadienyl ligands
are known: C5Me3Ph2,1 C5HPh4,2 and C5Ph5.3
Only (C5HPh4)2La{N(SiHMe2)2} (see Ref. 2) and
{(C5Ph5)Yb(THF)(C2Ph)}2 (see Ref. 3c) were structurꢀ
ally characterized.
nounced electronꢀdonating properties and influence the
Ln—ligand bond parameters.
To minimize the electronic effect of the substituents
on the electron density distribution in the complexes, we
chose Ph groups as substituents in the cyclopentadienyl
ligand. These groups have weak electronꢀwithdrawing
rather than electronꢀdonating properties and are also
bulky.
In the present study, we synthesized and investigated
the heteroleptic complex (1,3ꢀPh2C5H3)Lu(Ph4C2) and
its synthetic precursor (1,3ꢀPh2C5H3)LuCl2.
Earlier,4,5 we have reported the synthesis of homoleptic
lutetium and yttrium ateꢀcomplexes with the tetraꢀ
phenylethylene dianion containing the complex anion
[Ln(Ph4C2)2]– (Ln = Lu or Y) and the heteroleptic comꢀ
plex (C5H5)Lu(Ph4C2)(THF)2, in which the bisꢀη3ꢀallyl
coordination of the tetraphenylethylene dianion was obꢀ
served. In the latter complex, the lutetium atom is addiꢀ
tionally coordinated by two THF molecules. Conseꢀ
quently, the cyclopentadienyl and tetraphenylethenide
ligands are insufficient to saturate the coordination sphere
of the metal atom. The widely used alkyl and trimethylsilyl
substituents in the cyclopentadienyl anion exhibit the proꢀ
Results and Discussion
The reaction of lutetium chloride with sodium
diphenylcyclopentadienide and disodium tetraphenylꢀ
ethylene in anhydrous THF produced the
(Ph2C5H3)Lu(Ph4C2)(THF) complex (1), which was isoꢀ
lated as a purple microcrystalline powder highly sensitive
to atmospheric moisture and oxygen (Scheme 1).
The structure of complex 1 was established by Xꢀray
diffraction (Fig. 1, Tables 1 and 2). A strong shift of the
absorption band of the coordinated tetraphenylethylene
dianion (λmax = 390 nm) to shorter wavelengths comꢀ
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1912—1918, October, 2007.
1066ꢀ5285/07/5610ꢀ1978 © 2007 Springer Science+Business Media, Inc.

Synthesis and structures of lutetium complexes
Russ.Chem.Bull., Int.Ed., Vol. 56, No. 10, October, 2007
1979
Scheme 1
C(16)
C(15)
C(17)
C(29)
C(30)
C(31)
C(4)
C(5)
C(14)
C(3)
C(1)
C(12)
C(2)
C(6)
C(13)
C(28)
C(27)
Lu(1)
C(24)
C(25)
C(26)
C(11)
C(7)
C(8)
C(9)
C(20)
C(23)
C(10)
C(46)
C(18)
C(21)
C(19)
C(43)
O(1)
C(37)
C(45)
C(22)
C(38)
C(44)
C(36)
C(32)
C(42)
C(41)
C(39)
C(40)
C(35)
C(34)
C(33)
LuCl3(thf)3 + Na[1,3ꢀPh2C5H3] + Na2[Ph4C2]
Fig. 1. Overall view of the complex (Ph2C5H3)Lu(Ph4C2)•THF
(6). The hydrogen atoms are omitted.
{(Ph2C5H3)Lu(Ph4C2)(THF)} + 3NaCl.
1
Reagents and conditions: i. 1)NaOEt, Et2O—EtOH,
2) PhCOCH2Br; ii. NaOH (dilut.), 80 °C, 5 h; iii. 1)PhLi,
2) HCl (dilut.); iv. NaH (excess), THF.
the electron density on the atoms of the Cp ring, which,
in turn, reduces the electron density on the lutetium catꢀ
ion and results in a strengthening of the Lu—(C2Ph4)
bond and, consequently, in a larger shift of the absorption
band of the tetraphenylethylene dianion.
The reaction under consideration affords two organoꢀ
lutetium byꢀproducts, viz., a red precipitate of the
[Na(THF)5][Lu(Ph4C2)2] complex (6% yield based on
lutetium) described in our earlier study4 and a colorless
substance, which was not isolated.
pared to the sodium and potassium adducts of tetraphenylꢀ
ethylene (λmax = 485 nm)6 is evidence for the strong coꢀ
ordination of the tetraphenylethylene dianion to the
Lu3+ cation.4 The shift of the absorption band in the
spectrum of complex 1 (∆λmax = 95 nm) is the maximum
of all the shifts observed in the spectra of lanthanide comꢀ
plexes with the tetraphenylethylene dianion, whereas the
smallest shift (75 nm) is observed for the complex with
the unsubstituted Cp ligand, (C5H5)Lu(Ph4C2)(THF)2.
Apparently, the introduction of Ph substituents decreases
The previously unknown 1,3ꢀdiphenylcyclopentaꢀ
dienyllutetium dichloride (Ph2C5H3)LuCl2(THF)3 (2) is,
most likely, an intermediate in the synthesis of 1 starting
from lutetium chloride. We synthesized complex 2 by the
Table 1. Selected bond lengths (d) in complex 1
Bond
d/Å
Bond
d/Å
Bond
d/Å
Bond
d/Å
C(18)—C(19)
Lu(1)—C(18)
Lu(1)—C(26)
Lu(1)—C(27)
C(18)—C(26)
C(26)—C(27)
C(27)—C(28)
C(28)—C(29)
C(29)—C(30)
C(30)—C(31)
C(26)—C(31)
C(1)—C(5)–Lu 2.316
centroid
Lu(1)—C(1)
Lu(1)—C(2)
Lu(1)—C(3)
1.503(4)
2.422(3)
2.637(3)
2.585(3)
1.445(4)
1.446(4)
1.402(4)
1.359(5)
1.416(5)
1.369(5)
1.429(5)
Lu(1)—C(4)
Lu(1)—C(5)
C(1)—C(6)
2.578(3)
2.568(3)
1.481(5)
1.487(4)
1.393(4)
1.387(5)
1.373(5)
1.394(5)
1.384(4)
1.413(5)
1.396(5)
1.387(5)
1.364(6)
1.395(5)
1.390(5)
1.386(5)
Lu(1)—O(1)
Lu(1)—C(19)
Lu(1)—C(32)
Lu(1)—C(37)
C(19)—C(32)
C(32)—C(37)
C(36)—C(37)
C(35)—C(36)
C(34)—C(35)
C(33)—C(34)
C(32)—C(33)
C(1)—C(2)
2.269(2)
2.462(3)
2.641(3)
2.538(3)
1.426(4)
1.431(5)
1.410(4)
1.365(5)
1.406(5)
1.361(5)
1.440(4)
1.413(4)
1.428(4)
1.409(4)
1.401(4)
C(1)—C(5)
1.434(5)
1.478(4)
1.491(5)
1.395(5)
1.372(5)
1.388(5)
1.383(5)
1.385(5)
1.405(5)
1.406(5)
1.386(5)
1.362(5)
1.392(5)
1.393(5)
1.383(5)
C(3)—C(12)
C(19)—C(38)
C(38)—C(43)
C(42)—C(43)
C(41)—C(42)
C(40)—C(41)
C(39)—C(40)
C(38)—C(39)
C(12)—C(13)
C(13)—C(14)
C(14)—C(15)
C(15)—C(16)
C(16)—C(17)
C(12)—C(17)
C(18)—C(20)
C(20)—C(21)
C(21)—C(22)
C(22)—C(23)
C(23)—C(24)
C(24)—C(25)
C(20)—C(25)
C(6)—C(7)
C(7)—C(8)
C(8)—C(9)
C(9)—C(10)
C(10)—C(11)
C(6)—C(11)
C(2)—C(3)
C(3)—C(4)
C(4)—C(5)
2.625(3)
2.639(3)
2.645(3)

1980
Russ.Chem.Bull., Int.Ed., Vol. 56, No. 10, October, 2007
Roitershtein et al.
Table 2. Selected bond angles in complex 1
Scheme 2
Na(Ph2C5H3) + LuCl3(THF)3
Angle
Value
(Ph2C5H3)LuCl2(THF)3 + NaCl.
Bond angle
ω/deg
2
C(18)—C(19)—C(32)
C(19)—C(18)—C(26)
C(18)—C(26)—C(27)
C(19)—C(32)—C(37)
C(19)—C(32)—C(33)
C(18)—C(26)—C(31)
C(33)—C(32)—C(37)
C(27)—C(26)—C(31)
C(32)—C(19)—C(38)
C(18)—C(19)—C(38)
C(19)—C(18)—C(20)
C(19)—C(18)—C(20)
C(18)—C(19)—C(38)
C(19)—C(38)—C(43)
C(18)—C(20)—C(21)
C(39)—C(38)—C(43)
C(21)—C(20)—C(25)
C(20)—C(18)—C(26)
118.7(3)
115.8(3)
120.2(3)
121.6(3)
123.7(3)
125.7(3)
114.6(3)
114.0(3)
120.4(3)
119.0(3)
120.1(3)
120.1(3)
119.0(3)
120.8(3)
120.5(3)
116.6(3)
116.4(3)
122.5(3)
idene fragment), and one tetrahydrofuran molecule. The
interaction between the tetraphenylethylene dianion and
the lutetium cation can be best described as the bisꢀallyl
η6ꢀcoordination of the tetraphenylethylene dianion analoꢀ
gous to that found in the [Na(diglyme)2][Lu(Ph4C2)2]
and (C5H5)Lu(Ph4C2)(THF)2 complexes.4
In complex 1, the Lu—C1, Lu—C2, and Lu—C3
distances (Table 3) are similar to those found4 in
the [Na(diglyme)2][Lu(Ph4C2)2](THF)0.5 (3) and
{CpLu(Ph4C2)(DME)}(DME) (4) complexes. The genꢀ
eral atomic numbering of the carbon atoms in the comꢀ
plexes with the tetraphenylethylene ligand is given below.
Dihedral angle
C(11)—C(6)—C(1)—C(2)
C(13)—C(12)—C(3)—C(2)
ϕ/deg
11.5(5)
3.0(5)
C(21)—C(20)—C(18)—C(19) 20.5(5)
C(27)—C(26)—C(18)—C(19) 18.6(4)
C(33)—C(32)—C(19)—C(18) 166.9(3)
C(39)—C(38)—C(19)—C(18) 141.8(3)
In complex 1, only one THF molecule is coordinated
to lutetium. The coordination number of lutetium is 8,
which is lower than that in complex 4 (coordination numꢀ
ber is 9). The structures of 1 and 3 are most suitable for a
comparison because the coordination number of Lu in
both complexes is 8. In complex 1, the Lu—C2 distances
are slightly longer, whereas the Lu—C1 distances are
shorter than those in 3 (average Lu—C2 distances are
2.639 and 2.619 Å and the average Lu—C1 distances are
2.442 and 2.466 Å in 1 and 3, respectively). The pairwise
comparison of the Lu—C1, Lu—C2, and Lu—C3 distances
reaction of sodium 1,3ꢀdiphenylcyclopentadienide with
lutetium chloride trisꢀtetrahydrofuranate LuCl3(THF)3 in
THF (Scheme 2). Complex 2 was isolated as a colorless
crystalline compound, which is readily soluble in THF
and toluene and decomposes in air.
In complex 1, lutetium is coordinated by five carbon
atoms of the cyclopentadienyl ring, six atoms of the
tetraphenylethylene dianion (ipsoꢀ and orthoꢀcarbon atoms
of the aromatic rings and the carbon atoms of the ethylꢀ
Table 3. Selected bond lengths in the lutetium complexes with the tetraphenylethylene dianion*
Bond
1
3
4
C1—C1´
Ln—C1
Ln—C2
Ln—C3
C1—C2
C2—C3
C3—C4
C4—C5
C5—C6
C6—C7
C2—C7
C1—C8
1.503(4)
1.507(3)
2.481(2)
1.507(3)
2.441(2)
1.507(5)
2.422(3)
2.462(3)
2.641(3)
2.538(3)
1.426(4)
1.431(5)
1.410(4)
1.365(5)
1.406(5)
1.361(5)
1.440(4)
1.491(5)
2.478(2)
2.615(2)
2.524(1)
1.446(3)
1.446(3)
1.404(3)
1.379(3)
1.410(3)
1.379(3)
1.424(3)
1.480(3)
2.463(2)
2.607(2)
2.588(2)
1.438(3)
1.436(3)
1.406(3)
1.374(3)
1.405(4)
1.372(3)
1.440(3)
1.481(3)
2.493(3)
2.470(3)
2.763(3)
2.723(4)
1.443(5)
1.418(5)
1.397(5)
1.378(5)
1.405(5)
1.372(5)
1.435(5)
1.483(4)
2.637(3)
2.585(3)
1.445(4)
1.446(4)
1.402(4)
1.359(5)
1.416(5)
1.369(5)
1.429(5)
1.487(4)
2.643(2)
2.581(2)
1.438(3)
1.440(3)
1.405(3)
1.372(3)
1.411(3)
1.370(3)
1.438(3)
1.485(3)
2.610(2)
2.567(2)
1.434(2)
1.443(3)
1.404(3)
1.378(3)
1.404(3)
1.372(3)
1.435(3)
1.482(3)
2.703(3)
2.665(4)
1.435(5)
1.437(5)
1.402(5)
1.383(5)
1.378(5)
1.372(5)
1.428(5)
1.484(4)
* The atomic numbering scheme corresponds to the structural formula presented above.

Synthesis and structures of lutetium complexes
Russ.Chem.Bull., Int.Ed., Vol. 56, No. 10, October, 2007
1981
C(15)
in compounds 1 and 4 shows that these distances in comꢀ
plex 4 are longer than those in 1 due to the higher coordiꢀ
nation number. In heteroleptic complexes 1 and 4 (taking
into account the 0.055 Å difference between the ionic
radii of Lu3+ for the coordination numbers 9 and 8), the
Lu—C1 distances are shorter than those in homoleptic
complex 3 due, apparently, to the higher steric crowding
of 1 compared to that of 4 and even of 3. The tetraꢀ
phenylethylene dianion in complex 1, like that in 4, is
coordinated asymmetrically. One of the Lu—C3 distances
(Lu—C(37)) is 0.047 Å shorter than the opposite distance
(Lu—C(27)). Interestingly, the opposite situation is obꢀ
served for the corresponding Lu—C1 distances (Lu—C(18)
bond is 0.040 Å shorter than the Lu—C(19) bond).
C(14)
C(10)
C(13)
C(3)
C(11)
C(2)
C(6)
C(1)
C(5)
C(12)
C(16)
C(9)
C(17)
C(18)
C(7)
C(8)
C(4)
C(26)
C(27)
Lu(1)
C(19)
Cl(1)
O(3)
C(29)
O(1)
Cl(2)
O(2)
C(28)
C(21)
C(20)
C(25)
C(24)
C(22)
C(23)
It is of interest to follow changes in the structure of 1
in going from the crystalline state to solution. However,
1
the complex character of the H and 13C NMR spectra
Fig. 2. Overall view of the complex (Ph2C5H3)LuCl2•3THF (5).
did not allow us to make an unambiguous assignment for
all signals. Nevertheless, the 1H and 13C NMR and
The hydrogen atoms are omitted.
1
COSY H—1H spectroscopic data confirm the presence
C(1)
C(2)
C(3)
C(5)
C(4)
of five nonequivalent protons in the Ph group of the
tetraphenylethylene dianion coordinated to lutetium. The
spectroscopic data suggest that several exchange processes
proceed in a solution of this compound. To reveal the
exchange processes and estimate their activation paramꢀ
eters, we recorded the 2D 1H EXSY NMR spectrum. The
spectrum showed that two dynamic processes with similar
activation energies (69.7 0.8 and 71.3 0.8 kJ mol–1) proꢀ
ceed in a THF solution of 1 due to the hindered rotation
of the Ph rings. Earlier,4 we have observed the hindered
rotation of one of the Ph rings of the tetraphenylethylene
ligand in complex 4. Presumably, the dynamic processes
in complex 1 are associated with the hindered rotation of
both the Ph groups of the tetraphenylethenide ligand and
the substituted cyclopentadienyl anion.
C(16)
C(17)
Lu(1)
Cl(2)
O(3)
C(9)
C(8)
O(1)
C(14)
C(15)
Cl(1)
C(6)
C(7)
O(2)
C(13)
C(10)
C(12)
C(11)
In spite of the fact that several lutetium monoꢀ
cyclopentadienyl complexes have been described,1,3a,7,8
Lu(C5H5)(O3SCF3)2(THF)3 is the only structurally charꢀ
acterized LuCp´X2ꢀtype lutetium complex.9 The
(C5H5)LuCl2(THF)3 complex (5) is most useful for a
comparison of the structural parameters of complexes 1,
2, and 4. However, the structure of this complex was
unknown10 at the beginning of the present study. Hence,
we determined the structure of 5 by Xꢀray diffraction.
The structures of the (Ph2C5H3)LuCl2(THF)3 (2) and
Lu(C5H5)Cl2(THF)3 (5) complexes (Figs 2 and 3, Tables 4
and 5) are similar to those of other lanthanide monocycloꢀ
pentadienyl complexes LnCp´X2(THF)3. The lutetium
cation is in a pseudooctahedral environment with the coꢀ
ordination number 8. The cyclopentadienyl ring is η5ꢀcoꢀ
ordinated to the lutetium cation. The chloride anions are
in the trans positions with respect to each other. The
coordinated THF molecules are in the mer positions.
The Lu—O(2) distances between the lutetium atom
and the oxygen atom of tetrahydrofuran coordinated in
Fig. 3. Overall view of the complex (C5H5)LuCl2•3THF (7).
The hydrogen atoms are omitted.
the trans position to the cyclopentadienyl ring are 0.096 Å
(for 2) and 0.083 Å (for 5) longer than the Lu—O(1) and
Lu—O(3) distances due, presumably, to the deviation of
the lutetium cation by 0.547 Å (for 2) and 0.542 Å (for 5)
from the Cl(1),Cl(2),O(1),O(3) plane toward the cycloꢀ
pentadienyl ring. An analogous deviation of the lanthanide
atom toward the cyclopentadienyl ligand by 0.53 Å
(yttrium) and 0.68 Å (cerium) and an elongation of the
Ln—OTHF bonds were observed for the CpEuCl2(THF)3
(see Ref. 10) and (C5H5)LnX2(THF)3 (X = Cl, Ln = Nd,
Sm, Gd, Ho, Er, Yb, Y; X = Br, Ln = Yb; X = I,
Ln = Tm)11a—i compounds and for the substituted cycloꢀ
pentadienyl derivatives Cp´LnX2(THF)3.11k—m In comꢀ
plexes 2 and 5, the Lu—O(1) and Lu—O(3) distances are
in the range characteristic of the Lu—OTHF distances in
the lutetium bisꢀcyclopentadienyl complexes Cp´2LuX•L

1982
Russ.Chem.Bull., Int.Ed., Vol. 56, No. 10, October, 2007
Roitershtein et al.
Table 4. Selected bond lengths (d) in complexes 2 and 5
Bond
d/Å
Bond
d/Å
Bond
d/Å
Bond
d/Å
2
5
2
2
5
2
Lu—Cl(1)
Lu—Cl(2)
C(1)—C(5)–Lu
centroid
2.584(1) 2.6024(7) C(1)—C(6)
2.579(1) 2.6004(7) С(6)—С(7)
С(7)—С(8)
1.475(5) Lu—O(1)
1.392(6) Lu—O(2)
1.382(6) Lu—O(3)
2.330(3) 2.318(2) C(3)—C(12)
2.421(3) 2.396(2) С(12)—С(13) 1.399(6)
2.321(3) 2.309(2) С(13)—С(14) 1.403(6)
1.474(5)
2.389
2.354
С(8)—С(9)
1.383(7) C(1)—C(2) 1.428(6) 1.414(4) С(14)—С(15) 1.372(6)
Lu—C(1)
Lu—C(2)
Lu—C(3)
Lu—C(4)
Lu—C(5)
2.672(4) 2.661(3)
2.672(4) 2.636(3)
2.709(4) 2.624(3)
2.673(4) 2.627(3)
2.648(4) 2.661(3)
С(9)—С(10) 1.373(7) C(2)—C(3) 1.416(5) 1.408(4) С(15)—С(16) 1.381(7)
С(10)—С(11) 1.376(6) C(3)—C(4) 1.418(6) 1.407(4) С(16)—С(17) 1.384(6)
С(6)—С(11) 1.420(6) C(4)—C(5) 1.385(6) 1.410(4) С(12)—С(17) 1.399(5)
C(1)—C(5) 1.420(5) 1.406(4)
Table 5. Selected angles in complexes 2 and 5
with the coordination number 8 (Table 6). The Lu—OTHF
distances in complex 5 are similar to those in the
(C5H5)Lu(O3SCF3)2(THF)3 complex. In compound 2,
these distances are somewhat longer. The Lu—Cl disꢀ
tances in complexes 2 and 5 are 0.06—0.10 Å longer than
the corresponding distances in the alkylꢀ and trimethylꢀ
silylꢀsubstituted lutetium bisꢀcyclopentadienyl complexes
LuCp´2Cl(THF). In complex 2, the Lu—C distance is the
longest of all lutetium complexes with the coordination
number 8, which is apparently associated with the steric
influence of the diphenylcyclopentadienyl ligand. A comꢀ
parison of the average Lu—C(Cp) distances in complexes 2
(2.675 Å) and 1 (2.611 Å) and in complexes 5 (2.641 Å)
and 4 (2.593 Å) revealed the expected elongation of the
Lu—Cp bonds in the presence of bulky substituents in
the Cp ring, as well as the unexpected, at first glance,
shortening of the Lu—Cp bonds upon the replacement
of two chloride ligands by the bulkier tetraphenylethenide
ligand. The latter fact remains unclear. Probably, the forꢀ
malism, which we used to compare the structural data
and which assumes that the tetraphenylethylene dianion
is fourꢀcoordinated, does not provide an adequate deꢀ
scription of systems containing organic dianions as ligands.
Angle
ϕ/deg
2
5
Cl(1)—Lu(1)—Cl(2)
155.82(3)
154.96(2)
89.51(5)
77.47(5)
86.79(5)
85.33(5)
77.52(5)
87.18(5)
75.14(7)
78.85(7)
153.92(7)
103.0
Cl(1)—Lu(1)—O(1)
Cl(1)—Lu(1)—O(2)
Cl(1)—Lu(1)—O(3)
Cl(2)—Lu(1)—O(1)
Cl(2)—Lu(1)—O(2)
Cl(2)—Lu(1)—O(3)
O(1)—Lu(1)—O(2)
O(2)—Lu(1)—O(3)
84.37(8)
78.39(8)
87.95(7)
87.60(7)
77.60(8)
88.71(8)
77.2(1)
75.3(1)
152.4(1)
105.2
177.4
102.3
102.7
101.5
23.5
11.7
O(1)—Lu(1)—O(3)
C(1)—C(5)–Lu–O(1) centroid
C(1)—C(5)–Lu–O(2) centroid
C(1)—C(5)–Lu–O(3) centroid
C(1)—C(5)–Lu–Cl(1) centroid
C(1)—C(5)–Lu–Cl(2) centroid
С(1)—С(5)/C(6)—C(11)*
С(1)—С(5)/С(12)—С(17)*
178.1
102.9
103.1
102.0
* The dihedral angles between the planes of the cyclopentadienyl
ring and the phenyl groups in complex 2.
Table 6. Bond lengths (d) in some lutetium cyclopentadienyl complexes
Complex
Coordiꢀ
nation
number
d/Å
Reference
Lu—CCp (aver.)
Lu—Centroid Lu—Cl
Lu—OTHF (aver.)
Lu(C5H5)2Cl(THF)
Lu(C5Me5)2Cl(THF)
8
8
8
8
8
8
8
8
8
9
2.56
2.62
2.61
2.61
2.60
2.62
2.64
2.68
2.61
2.59
2.69
2.29 (aver.)
2.34 (aver.)
2.32
2.50
2.52
—
—
2.53
—
2.60
2.58
—
—
—
2.27
2.34
2.31
2.31
12
13
14
14
15
9
*
*
*
4
Lu(TMS2C5H3)2I(THF)Lu(TMS2C5H3)
(TMSC5H4)I(THF)
2.32
2.30
2.34
2.35
2.39
2.32
2.30
6
Lu(C5Me5)(η ꢀC5H4C2H4SPh)Cl
—
Lu(C5H5)(O3SCF3)2(THF)3
Lu(C5H5)Cl2(THF)3
2.30, 2.37 (transꢀCp)
2.31, 2.40 (transꢀCp)
2.33, 2.42 (transꢀCp)
2.27
2.42 (ODME
2.39
Lu(Ph2C5H3)Cl2(THF)3
Lu(Ph2C5H3)(Ph4C2)(THF)
Lu(C5H5)(Ph4C2)(DME)
)
5
Lu(η ꢀC5H5)3(THF)
10
2.42 (aver.)
16
* The present study.

Synthesis and structures of lutetium complexes
Russ.Chem.Bull., Int.Ed., Vol. 56, No. 10, October, 2007
1983
tion from ethanol and vacuum sublimation. Sodium 1,3ꢀdiꢀ
phenylcyclopentadienide was prepared by the metallation of a
mixture of isomers of diphenylcyclopentadiene with excess soꢀ
dium hydride in THF. The 1H and 13C NMR spectra were
recorded on Bruker WMꢀ250, Bruker AMꢀ300, and Bruker
DRXꢀ500 instruments. The electronic absorption spectra were
measured on a Specord 50PC spectrophotometer in THF in
sealed evacuated apparatus. The lutetium content in the samples
was determined by the direct complexometric titration using the
Xylenol Orange indicator.
It is also cannot be ruled out that the shortening of
the Lu—Cp bonds in this case is associated with the
electron density transfer from the dianionic ligand
through the metal atom to the antibonding orbital of the
Cp ligand.
To conclude, we synthesized the previously unavailꢀ
able lutetium complexes with the diphenylcyclopentaꢀ
dienyl ligand. A comparison of the structural parameters
of the complexes with the general formulas Cp´LnCl2 and
Cp´Ln(Ph4C2) (Cp´ = C5H5 or Ph2C5H3) showed that
the introduction of the electronꢀrich tetraphenylethylene
dianion into organolanthanide compound leads to changes
in the Ln—Cp´ bond parameters.
(1,3ꢀDiphenylcyclopentadienide)(1,1´,2,2´ꢀtetraꢀ
5
phenylethenediide)lutetium tetrahydrofuranate, (η ꢀ1,3ꢀ
6
Ph2C5H3)Lu(η ꢀPh4C2)(THF) (1). A solution of sodium 1,3ꢀdiꢀ
phenylcyclopentadienide in THF (40 mL), which was prepared
from diphenylcyclopentadiene (0.871 g, 3.99 mmol) and sodium
hydride (0.356 g, 15 mmol), was added with stirring to a suspenꢀ
sion of LuCl3•3THF (1.980 g, 3.99 mmol) in THF (20 mL) for
30 min. The reaction mixture was stirred for 2 days. Then a
solution of disodium tetraphenylethylene, which was prepared
from tetraphenylethylene (1.330 g, 3.99 mmol), was added with
vigorous stirring for 3 h. The mixture was stirred for 2 days and
refluxed for 4 h, THF was removed in vacuo, the solid residue
was extracted with THF at room temperature (5×50 mL), and
the extract was concentrated. The purple finely crystalline preꢀ
cipitate was washed with a small amount of THF (3×3 mL),
dried in vacuo, and extracted with toluene at room temperature.
The toluene extract was concentrated, and the dry residue was
washed with toluene (3×15 mL) and dried in vacuo. The product
was recrystallized from a small amount of THF and dried
in vacuo. Compound 1 was obtained in a yield of 1.609 g (46%).
Found (%): Lu, 21.89. C47H41OLu. Calculated (%): Lu, 21.95.
Experimental
All the complexes under study are extremely sensitive to
atmospheric oxygen and moisture. Hence, the synthesis and
preparation of samples were carried out in sealed evacuated
Schlenkꢀtype apparatus. The solvents were purified and stored
according to procedures described earlier.4 The LuCl3(THF)3
complex was isolated by extraction of anhydrous lutetium triꢀ
chloride, which was prepared from the hexahydrate,17 with hot
THF. Tetraphenylethylene (Acros, 98%) was purified by reꢀ
crystallization from toluene and dried in vacuo. Diphenylꢀ
cyclopentadiene was synthesized according to a known proceꢀ
dure18 in 27% yield (as a mixture of isomers of 1,3ꢀ and
1,4ꢀdiphenylcyclopentadiene) and purified by recrystallizaꢀ
Table 7. Crystallographic data for complexes 1, 2, and 5
Parameter
1
2
5
Molecular formula
Empirical formula
Molecular weight
Temperature/K
Crystal dimensions
Crystal system
Space group
a/Å
b/Å
c/Å
Lu(C5H3Ph2)Cl2(THF) Lu(C5H3Ph2)(C2Ph4)(THF)
Lu(C5H5)Cl2(THF)3
C17H29Cl2LuO3
527.27
C29H37Cl2LuO3
679.46
C47H41LuO
796.77
120
110
100
0.40×0.20×0.20
Orthorhombic
P212121
9.6763(7)
12.8638(9)
22.053(2)
90.0
0.32×0.24×0.20
Monoclinic
P21/n
11.4228(6)
23.078(1)
13.2685(6)
97.425(1)
3468.5(3)
4
0.28×0.22×0.20
Monoclinic
P21/n
7.7535(4)
16.8153(9)
14.6973(8)
95.419(1)
1907.6(2)
4
α/deg
V/Å3
2745.0(3)
4
Z
dcalc/g cm–3
1.644
1.526
1.836
Linear absorption, µ/cm–1
θꢀScan range, deg
Number of measured reflections
Number of independent reflections
Rint
38.19
1.83—29.50
24536
7617
0.0348
28.83
2.52—29.00
23913
9041
0.0378
54.66
1.84—29.50
11870
5258
0.0270
Number of reflections with I > 2σ(I )
Number of variables
R1 based on reflections with I > 2σ(I )
wR2 based on all reflections
GOOF based on F 2
6580
317
2.89
6.38
6510
442
3.38
6.26
4509
208
2.27
4.94
1.009
1.040
0.992

1984
Russ.Chem.Bull., Int.Ed., Vol. 56, No. 10, October, 2007
Roitershtein et al.
Electronic absorption spectrum (THF) λmax/nm: 320, 390,
560. 1H NMR (500 MHz, THFꢀd8), δ: 4.59—4.63 (m, 1 H);
5.82—5.86 (m, 2 H); 5.88—5.90 (m, 1 H); 5.95—5.99 (m, 1 H);
6.53—6.58 (m, 1 H); 6.61—6.64 (m, 1 H); 6.69—6.74 (m, 1 H);
6.77—6.82 (m, 1 H); 6.87—6.93 (m, 2 H); 6.96—7.02 (m, 1 H);
7.03—7.08 (m, 2 H); 7.14—7.22 (m, 6 H); 7.22—7.27 (m, 1 H);
7.27—7.33 (m, 2 H); 7.34—7.42 (m, 4 H); 7.50—7.54 (m, 1 H);
7.58—7.62 (m, 2 H); 7.68—7.72 (m, 2 H); 7.93—7.98 (m, 1 H).
13C{1H} NMR (75 MHz, THFꢀd8), δ: 88.4, 88.6, 95.0, 95.5,
102.3, 111.5, 112.2, 112.5, 114.5, 119.5, 122.3, 122.4, 122.5,
125.3, 125.8, 126.7, 126.8, 127.9, 128.1, 128.3, 128.4, 128.7,
129.35, 129.36, 129.6, 133.3, 133.9, 135.7, 136.5, 138.9, 140.6,
141.0, 143.1, 144.1, 144.9.
Darkꢀred crystals of the byꢀproduct insoluble in toluene
were washed three times with toluene and recrystallized
from THF. The lutetium content, the electronic absorption specꢀ
trum, and the 1H and 13C NMR spectra of the product were
identical to those for the [Na(THF)5][Lu(Ph4C2)2] complex
described earlier.4 The product was obtained as red crystals in a
yield of 0.302 g (0.247 mmol, 6% based on lutetium).
This study was financially supported by the Russian
Foundation for Basic Research (Project No. 04ꢀ03ꢀ
32737a).
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[1,3ꢀDiphenylcyclopentadienidelutetium dichloride] trisꢀ
5
tetrahydrofuranate, (η ꢀ1,3ꢀPh2C5H3)LuCl2(THF)3 (2). The
LuCl3(THF)3 complex (1.755 g, 3.53 mmol) was added with
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1
culated (%): Lu, 25.75. H NMR (250 MHz, THFꢀd8), δ: 6.62
(d, 2 H); 7.00—7.12 (m, 3 H); 7.23—7.35 (t, 4 H); 7.77 (d, 4 H).
13C{1H} NMR (75 MHz, THFꢀd8), δ: 110.4, 110.8, 126.1, 126.6,
127.0, 129.5, 138.9.
[Cyclopentadienidelutetium dichloride] trisꢀtetrahydroꢀ
5
furanate, (η ꢀC5H5)LuCl2(THF)3 (5). Complex 5 was syntheꢀ
sized according to a known procedure15 from lutetium chloꢀ
ride trisꢀtetrahydrofuranate and sodium cyclopentadienide in
51% yield. 1H NMR (250 MHz, THFꢀd8, 297 K), δ: 6.15 (s).
13C{1H} NMR (63 MHz, THFꢀd8), δ: 111.1.
Xꢀray diffraction study of complexes 1, 2, and 5. Single crysꢀ
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Samples were prepared for the Xꢀray diffraction study according
to a procedure described earlier.19 Xꢀray diffraction data for
compounds 1 and 2 were collected on a Smart 1000 CCD
diffractometer (λ(MoꢀKα) = 0.71072 Å); for compound 5, on a
Smart APEX II CCD diffractometer (λ(MoꢀKα) = 0.71072 Å).
The crystallographic data and the principal refinement statistics
for complexes 1, 2, and 5 are given in Table 7. Semiempirical
absorption corrections were applied based on equivalent reflecꢀ
tions with the use of the SADABS program.20 The structures
were solved by direct methods and refined by the fullꢀmatrix
leastꢀsquares method based on F 2 with anisotropic displaceꢀ
ment parameters for nonhydrogen atoms and isotropic displaceꢀ
ment parameters for hydrogen atoms with the use of the
SHELXTLꢀ97 program package. All hydrogen atoms in the strucꢀ
tures of 1, 2, and 5 were positioned geometrically and refined
using a riding model. In all structures, uncoordinated solvent
molecules are absent.
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Z. Anorg. Allg. Chem., 2003, 629, 1184.

Synthesis and structures of lutetium complexes
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1985
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Received December 29, 2006;
in revised form June 8, 2007