Polyphenylcyclopentadienyl complexes of rare earth elements

Article abstract of DOI:10.1007/s11172-012-0238-8

Reaction of LnCl₃(thf) _x (Ln = Y, La, Yb, Lu) with NaCp^Phn (Cp^Phn = 1,3-Ph₂C₅H ₃, 1,2,4-Ph₃C₅H₂, Ph ₄C₅H) leads to formatio

Full text of DOI:10.1007/s11172-012-0238-8

Russian Chemical Bulletin, International Edition, Vol. 61, No. 9, pp. 1726—1732, September, 2012
1726
Polyphenylcyclopentadienyl complexes of rare earth elements
D. M. Roitershtein,a,b M. E. Minyaev,a,c A. A. Mikhaylyuk,a,d K. A. Lyssenko,c I. V. Glukhov,c P. A. Belyakovb
aL.Ya. Karpov Institute of Physical Chemistry,
6 buld., 3ꢀ1/12, per. Obukha, 105064 Moscow, Russian Federation.
Fax: +7 (495) 917 2490
bN. D. Zelinsky Institute of Organic Chemistry of Russian Academy of Sciences,
47 Leninsky prosp., 119991 Moscow, Russian Federation.
Fax:+7 (499) 135 5328. Eꢀmail: roiter@server.ioc.ac.ru
cA. N. Nesmeyanov Institute of Organoelement Compounds of Russian Academy of Sciences,
28 ul. Vavilova,119991 Moscow, Russian Federation.
Fax: +7 (499) 135 5085
dA. V. Topchiev Institute of Petrochemical Synthesis of Russian Academy of Sciences,
21 Leninsky prosp., 119991 Moscow, Russian Federation.
Fax: +7 (495) 633 8520
Reaction of LnCl3(thf)x (Ln = Y, La, Yb, Lu) with NaCpPhn (CpPhn = 1,3ꢀPh2C5H3,
1,2,4ꢀPh3C5H2, Ph4C5H) leads to formation of monocyclopentadienyl dichloride complexes
Yb(Ph2C5H3)Cl2(thf)3 (1), Ln(Ph3C5H2)Cl2(thf)3 (Ln = Y (2), Lu (3)), La(Ph4C5H)Cl2(thf)3 (4).
Molecular structures of 1, 2 and the polynuclear complex [(Ph3C5H2)3Lu4(Cl)7(O)(thf)3] (5),
which is a partial hydrolysis product of 3, have been established by the Xꢀray method.
Keywords: organolanthanides, yttrium, lanthanum, ytterbium, lutetium, diphenylcycloꢀ
pentadiene, triphenylcyclopentadiene, tetraphenylcyclopentadiene, phenylcyclopentadienyl
complexes.
Intensive progress of organolanthanide chemistry is reꢀ
The goal of the present work is synthesis, structural
studies of rare earth metals complexes with polyphenyl
substituted cyclopentadienyl ligands Ln(C5H5–nPhn)ꢀ
Cl2(thf)3 (n = 2—4) and study of the influence of steric
and electronic effects of the phenyl substituents in the
cyclopentadienide anion on Ln—Cp bond peculiarities in
comparison with other monocyclopentadienyl complexes,
e. g., with dihalide complexes Ln(C5H5–nRn)Hal2(thf)3.
sulted from the fundamental interest to the nature of the
lanthanide—carbon bond in different types of organolanꢀ
thanides, possible applications of 4fꢀelement organic deꢀ
rivatives. Monocyclopentadienyl dichloride complexes
LnCpСl2(thf)3 were among the first explored organoꢀ
lanthanides, which were synthesized in 1960ꢀs.1,2 Analoꢀ
gous dichloride complexes with substituted cyclopentadiꢀ
enyl ligands attract one´s interest as convenient precursors
in synthesis of heteroleptic complexes LnCp´(L)х(solv)m
(solv is ꢀdonor ligand).
Results and discussion
Presently, cyclopentadienyl rare earth complexes with
trimethylsilyl and alkyl substituents in the cyclopentadieꢀ
nyl ligand and also indenyl and fluorenyl complexes of
rare earth metals have been studied. However, organolanꢀ
thanides with phenyl substituted cyclopentadienyl ligands
have been poorly studied so far. Crystal structures only of
a few polyphenylcyclopentadienyl rare earth complexes
have been established earlier: Lu(1,3ꢀPh2C5H3)Cl2(thf)3,3
Reaction of soduim 1,3ꢀdiphenylꢀ, 1,2,4ꢀtriphenylꢀ
and 1,2,3,4ꢀtetraphenylcyclopentadienides with lanꢀ
thanide and yttrium trichloride tetrahydrofuranates in 1:1
ratio in THF results in formation of corresponding monoꢀ
cyclopentadienyl dichloride rare earth complexes: Yb(1,3ꢀ
Ph2C5H3)Cl2(thf)3 (1), Ln(1,2,4ꢀPh3C5H2)Cl2(thf)3
(Ln = Y (2), Lu (3)), La(Ph4C5H)Cl2(thf)3 (4) (Scheme 1).
the complexes are obtained as lightꢀviolet (1) and colorꢀ
less (2—4) microcrystalline powders decomposing in air
and being readily soluble in THF and toluene.
1Н NMR spectra of complexes 2—4 appear to be nearly
uninformative due to a large number of overlapping sigꢀ
nals from magnetically nonequivalent phenyl ring proꢀ
tons. Thus, proton signals from cyclopentadienyl ring and
Lu(1,3ꢀPh2C5H3)(Ph4C2)(thf),3
[(1,2,4ꢀPh3C5H2)ꢀ
Nd(BH4)3]2[Mg(thf)6],4 (C5HPh4)2La{N(SiHMe2)2},5
{(C5Ph5)Yb(thf)(C2Ph)}2 (see. Ref. 6) and {C5(4ꢀBunꢀ
C6H4)5}2Ln (Ln = Sm, Yb).7 Dihalide complexes of rare
earth metals with triꢀ and tetraphenyl subtituted cycloꢀ
pentadienyl ligands are unknown.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1710—1716, September, 2012.
1066ꢀ5285/12/6109ꢀ1726 © 2012 Springer Science+Business Media, Inc.

Polyphenylcyclopentadienyl complexes
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 9, September, 2012
1727
Scheme 1
structures of compouns 1 and 2 (Figs 1 and 2) are similar
to other lanthanide cyclopentadienyl dihalide complexes
LnCp´Hal2(thf)3 with coordination number (CN) of 8 (see
Refs 2, 3). Compound 1 is isostructural with Lu(1,3ꢀPh2ꢀ
C5H3)Cl2(thf)3 (see Ref. 3). Phenyl ring rotation angles with
respect to the plane of the cyclopentadienyl ring are in the
range of 9.3—39.2 for complexes 1 and 2. The largest roꢀ
tation angles in compound 2 (31.2—39.2) are observed
for the phenyl rings at positions 1 and 2 of the 1,2,4ꢀtriꢀ
phenylcyclopentadienyl ligand. Cipso(Ph)—Cipso(Cp) bond
lengths in compounds 1 and 2 (1.445—1.484 Å) are slightꢀ
ly shorter than a single CꢀC bond length. Cipso(Ph) carbon
atoms are slightly out of the plane of the cyclopentadienyl
ring by 0.05—0.13 Å from the metal in complex 1 and by
0.07—0.28 Å in 2, locating away from the metal atom.
C
ipso(Ph)—Cipso(Cp)—Cpcentroid angles are in the range of
175.6—168.3 in complexes 1 and 2.
Crystallization of 3 from THF—pentane mixture alꢀ
lowed us to isolate poorly soluble in THF complex [{(5ꢀ
1,2,4ꢀPh3C5H2)Lu}3{Lu(thf)3}(3ꢀCl)(2ꢀCl)6(4ꢀ
O)](thf)2 (5), apparently formed as a result of partial hyꢀ
drolysis of 3. Its crystal structure was established by Xꢀray
diffraction method (Fig. 3, Tables 1 and 4). Four lutetium
cations in [(Ph3C5H2)3Lu4Cl7O(thf)3] are connected via
4ꢀoxygen atom and thus form a distorted tetrahedron
Lu4(4ꢀO). Atom Cl(1) is 3ꢀcoordinated with three luteꢀ
tium cations Lu(1), Lu(2), Lu(3) having CN of 8 and
being are 5ꢀcoordinated with 1,2,4ꢀtriphenylcyclopentaꢀ
dienyl ligands. The other chlorine atoms are 2ꢀbound to
Ln = Y (2), Lu (3)
phenyl groups are observed as complex multiplets at
6.9—7.4 (2), 6.8—7.4 (3) and 7.0—7.8 ppm (4) in 1H NMR
spectra.
Therefore, Xꢀray diffraction method was applied to
determine structures of 1 and 2 (Tables 1—3). Molecular
Table 1. Crystallographic data for complexes Yb(Ph2C5H3)Cl2(thf)3 (1), [Y(Ph3C5H2)Cl2(thf)3](thf)0.5 (2) and
[(Ph3C5H2)3Lu4Cl7O(thf)3](thf)2 (5)
Parameter
1
2
5
Empirical formula
Molecular mass
Т/K
Crystal system
Space group
a/Å
b/Å
c/Å
C29H37Cl2YbO3
677.53
100(2)
Orthorhombic
P212121
9.6450(9)
12.881(1)
21.987(2)
90
C37H45Cl2O3.50
705.54
100(2)
Monoclinic
P21/c
Y
C89H91Cl7Lu4O6
2204.65
100(2)
Monoclinic
P21/n
14.1202(12)
25.705(2)
23.345(3)
104.596(4)
8199.8(14)
4
23.500(5)
13.580(3)
21.030(4)
96.07(3)
6674(2)
4
/deg
V/Å3
2731.6(4)
4
1.647
Z
dcalc/g•cm–3
1.404
1.945
1.786
5.055
/mm–1
3.648
Range, /deg
1.83—29.00
21090
1.94—27.00
45672
1.20—28.50
85672
Number of measured reflections
Number of unique reflections
Rint (%)
7240
4.81
17044
—
20777
3.78
Number of reflections with I > 2(I)
Number of refined parameters
R1 (I > 2(I))
6349
317
3.16
4810
742
6.33
16714
950
2.70
wR2 (all parameters)
GOOF on F2
6.61
1.000
24.98
0.659
6.29
0.964

1728
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 9, September, 2012
Roitershtein et al.
Table 2. Selected bond lengths (d) in complexes 1 and 2a
C(16)
C(17)
C(12)
C(15)
C(10)
C(11)
C(2)
C(3)
C(4)
C(1)
C(6)
Bond
d/Å
C(9)
C(14)
C(8)
C(7)
1
2*
C(13)
C(5)
A
B
Cl(1)
Yb(1)
Ln—Cl(1)
Ln—Cl(2)
Ln—O(1)
Ln—O(2)
Ln—O(3)
Ln—C(1)
Ln—C(2)
Ln—C(3)
Ln—C(4)
Ln—C(5)
2.591(1)
2.583(1)
2.334(3)
2.416(3)
2.354(3)
2.683(4)
2.671(5)
2.700(4)
2.681(5)
2.653(5)
2.601(2)
2.560(2)
2.302(5)
2.490(5)
2.337(5)
2.727(7)
2.762(7)
2.720(7)
2.679(7)
2.621(7)
2.423
2.577(2)
2.598(2)
2.341(5)
2.484(5)
2.332(5)
2.739(8)
2.772(8)
2.692(8)
2.691(7)
2.662(7)
2.431
O(3)
O(1)
Cl(2)
O(2)
Fig. 1. Molecular structure of the complex 1. Hydrogen atoms
are omitted for clarity.
Centroid Cp—Ln 2.391
a Two crystallographically unique molecules.
C(14)
C(13)
C(12)
C(15)
C(16)
C(17)
C(2)
Table 3. Selected valent angles () in complexes 1 and 2a
C(8)
C(3)
C(9)
C(19)
C(7)
C(18)
C(20)
C(21)
Angle
/deg
C(6)
C(4)
C(11)
Cl(2)
C(23)
C(22)
C(10)
1
2*
C(1)
C(5)
Y(1)
A
B
O(3)
Cl(1)—Ln—Cl(2)
Cl(1)—Ln—O(1)
Cl(1)—Ln—O(2)
Cl(1)—Ln—O(3)
Cl(2)—Ln—O(1)
Cl(2)—Ln—O(2)
Cl(2)—Ln—O(3)
O(1)—Ln—O(2)
156.12(4)
88.05(8)
78.78(9)
84.13(8)
88.90(9)
77.55(9)
87.66(8)
75.1(1)
77.3(1)
152.3(1)
102.6
154.50(7) 152.48(8)
O(1)
83.7(1)
78.1(1)
90.2(1)
85.2(1)
77.2(1)
89.6(1)
78.6(2)
74.9(2)
153.6(2)
102.5
82.6(1)
77.6(1)
89.2(2)
83.7(1)
76.5(1)
92.9(1)
79.8(2)
74.6(2)
154.3(2)
103.6
Cl(1)
O(2)
Fig. 2. Structure of one of the two crystallographically unique
molecules of the complex 2. Hydrogen atoms are omitted for
clarity.
O(2)—Ln—O(3)
O(1)—Ln—O(3)
Centroid Cp—Ln—Cl(1)
Centroid Cp—Ln—Cl(2)
Centroid Cp—Ln—O(1)
Centroid Cp—Ln—O(2)
Centroid Cp—Ln—O(3)
101.2
102.1
176.9
105.5
102.6
103.2
Cambridge Structural Database (CSD)8 . Monoꢀ and polyꢀ
nuclear complexes which had each lanthanide atom being
coordinated to only one cyclopentadienyl ligand were takꢀ
en into consideration. Compounds with electron deficient
Ln—L—Ln bonds were excluded from the sample as well
as complexes with uncertain lanthanide coordination numꢀ
bers. Generally accepted formalism designates a metal catꢀ
ion coordination number to be equal to the number of
electron pairs donated to the metal10. Structures with
R1 > 10% have also been excluded. The final set of comꢀ
pounds consists of 426 crystal structures of complexes with
the composition mentioned above (603 crystallographiꢀ
cally independent fragments Ln3+—Cp´).
105.0
106.5
176.3
173.6
101.4
99.1
a Two crystallographically unique molecules.
metal atoms. Cation Lu(4) (C.N. is 7) is coordinated with
three THF molecules. The structural fragment Lu4(3ꢀ
Cl)(2ꢀCl)6(4ꢀO) possesses C3v symmetry. Complexes
[(5ꢀС5H9ꢀC5H4)3Er4(3ꢀCl)(2ꢀCl)6(4ꢀO)(thf)3] (see
Ref. 8) and [(5ꢀСH3ꢀC5H4)3Yb4(3ꢀCl)(2ꢀCl)6(4ꢀO)ꢀ
(thf)3] (see Ref. 9) have molecular structures analogous to 5.
In order to explore the influence of steric and/or elecꢀ
tronic effects of ligands on the interaction Ln3+—Cp´
(Cp´ is cyclopentadienyl anion or its substituted anaꢀ
logues), a number of structural parameters of such fragꢀ
ments were analysed for all monocyclopentadienyl comꢀ
plexes of yttrium and lanthanides(III) available from the
To our opinion, a more convenient comparison paraꢀ
meter is the difference between the values of Ln—Cpcentroid
distance and Ln3+ionic radii (see Ref. 11) of the corresꢀ
ponding lanthanide coordination number10: RCp
=
= d(Ln3+—Cpcentroid) – r(Ln3+). For example, the comꢀ

Polyphenylcyclopentadienyl complexes
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 9, September, 2012
1729
of was not wellꢀestablished within the sample, it can be
noted that the largest RCp values of were found for comꢀ
plexes with relatively low coordination numbers (C.N. of
5 or 6) (Table 5). This might be due to the presence of
bulky ligands, which impose steric hindrance, and hence
increase the distance Ln—Cp´. The minimum RCp values
were found for complexes with C.N. of 8 or 9 having elecꢀ
tronꢀexcessive ligands, e.g., with cyclooctatetraene diꢀ
anion, and also in complexes with nitrate anion and
in polynuclear complexes {(5ꢀС5H5)12(3ꢀCl)24Sm12},
[(5ꢀС5Me5)Tm(NCCH3)6]I2 (see Table 5).
In case of cyclooctatetraene dianion, partial electron
density transfer from an electronꢀexcessive ligand through
the metal to the *ꢀantiꢀbonding orbital of the cyclopenꢀ
tadienyl ligand is one possible reason for lowering RCp
values. In case of significant decrease of the RCp values,
one may assume that the lanthanide—cyclopentadienyl
ligand bond has essentially covalent nature.
C(64)
C(47)
C(51)
C(50)
C(49)
C(48)
C(58)
C(18)
C(41)
C(27)
C(52)
C(4)
C(5)
Cl(1)
Cl(4)
C(28)
Cl(3)
C(1)
C(26)
Lu(3)
Lu(1)
O(1)
C(6)
C(25)
C(2)
C(12)
Lu(2)
C(3)
C(24)
Cl(5)
Cl(2)
Cl(7)
Cl(6)
Lu(4)
O(4)
C(35)
C(29)
O(2)
O(3)
If within the chosen sample only compounds
LnCp´X2(solv)m (X is halogen or analogues; m = 2, 3;
solv is ꢀdonor ligands, CN 7, 8; 38 crystal structures,
42 crystallographically independent molecules) were conꢀ
sidered, it was found that RCp values for this type of comꢀ
plexes vary in a narrow interval: from 1.21 to 1.31 Å.
This supports a similarity of the LnCp´bond nature in all
compounds of the LnCp´X2(solv)m type. The RCp values
for the complexes LnCp´X2(solv)m lie in the range of the
average RCp values for all monocyclopentadienyl complexꢀ
es of lanthanides (III) and yttrium of the sample.
For more correct analysis of the latter sample, the
structures with systematic errors (the absence of hydrogen
atoms in the crystallographic model) were excluded from
the sample. This resulted in reduction of sample to
26 compounds (29 crystallographically independent moꢀ
lecules), which revealed a correlation between increase of
RCp values and growth of both the number of bulky subꢀ
stituents in the cyclopentadienyl ligand and their steric
Fig. 3. Structure of the complex 5. Only ipsoꢀatoms of phenyl
groups are shown. Hydrogen atoms and uncoordinated THF
molecules are omitted for clarity.
plex Lu(5ꢀ1,3ꢀPh2C5H3)(6ꢀPh4C2)(thf) (see Ref. 3) has
CN (Lu)= 8, d(Lu—Cpcentroid) = 2.316 Å, r(Lu3+) = 1.117 Å
(see Ref. 11), RCp = d(Lu—Cpcentroid) – r(Lu3+) = 1.199 Å
values. If ionic radii values for some coordination numꢀ
bers were missing in the literature11, earlier described10
correction was applied in our calculations for extrapolaꢀ
tion of the ionic radii to the necessary coordination number.
Coordination numbers of Ln3+ in the sample from CSD
are within the range of 5—10. The RCp values for the comꢀ
plexes varied in the range from 1.08 to 1.42 Å. Although
the reliable correlation between RCp and the ligand nature
Table 4. Selected valent bond lengths (d) in the complex 5
Bond
d/Å
Bond
d/Å
Bond
d/Å
Lu(1)—Cl(1)
Lu(1)—Cl(2)
Lu(1)—Cl(3)
Lu(1)—Cl(6)
Lu(2)—Cl(1)
Lu(2)—Cl(2)
Lu(2)—Cl(4)
Lu(2)—Cl(5)
Lu(3)—Cl(1)
Lu(3)—Cl(3)
Lu(3)—Cl(4)
Lu(3)—Cl(7)
Lu(4)—Cl(5)
Lu(4)—Cl(6)
2.7646(9)
2.6109(9)
2.6498(9)
2.5855(9)
2.7899(9)
2.6355(9)
2.6009(9)
2.5884(9)
2.7524(9)
2.6274(9)
2.6456(9)
2.5986(9)
2.6735(9)
2.7242(9)
Lu(4)—Cl(7)
Lu(1)—O(1)
Lu(2)—O(1)
Lu(3)—O(1)
Lu(4)—O(1)
Lu(4)—O(2)
Lu(4)—O(3)
Lu(4)—O(4)
Lu(1)—C(1)
Lu(1)—C(2)
Lu(1)—C(3)
Lu(1)—C(4)
Lu(1)—C(5)
2.6632(9)
2.266(2)
2.263(2)
2.253(2)
2.133(2)
2.328(3)
2.297(3)
2.385(3)
2.653(3)
2.701(3)
2.657(3)
2.624(3)
2.588(3)
Lu(2)—C(24)
Lu(2)—C(25)
Lu(2)—C(26)
Lu(2)—C(27)
Lu(2)—C(28)
Lu(3)—C(47)
Lu(3)—C(48)
Lu(3)—C(49)
Lu(3)—C(50)
Lu(3)—C(51)
Centroid C(1—5)—Lu(1)
Centroid C(24—28)—Lu(2)
Centroid C(47—51)—Lu(3)
2.634(3)
2.691(3)
2.653(3)
2.608(3)
2.570(3)
2.681(4)
2.660(4)
2.597(4)
2.619(4)
2.638(4)
2.350
2.341
2.348

1730
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 9, September, 2012
Roitershtein et al.
Table 5. RCp values for some monocyclopentadienyl complexes of lantanides(III) and yttrium
Complex
CSD code8
C.N.
RCp/Å
Reference
Compounds with maximum RCp
5
2
3
{[ ꢀС5Me4(TMS)]4( ꢀNCH—Ph)4( ꢀNEt)2Y4}
FEVQIH
JAYMIF
JAYMOL
FEVQON
CUTGUT
AVEXII
KASYIM
KADCUN
VULKOC
*
5
5
6
6
6
6
5
6
1.395, 1.424
1.422
1.418
1.395—1.414
1.413
1.412, 1.413
1.394, 1.404
1.402
12
13
13
12
14
15
16
17
18
5
1
{( ꢀС5Me5)Ce[ ꢀCH(TMS)2]2}
5
1
{( ꢀС5Me5)Ce[ ꢀN(TMS)2]2}
5
3
{[ ꢀС5Me4(TMS)]4( ꢀNEt)4Y4}
5
1
[Li(tmeda)2][( ꢀС5Me5)La( ꢀMe)3]
5
3
{[ ꢀС5Me4(TMS)]4( ꢀNCH2Ph)41Lu4}
{( ꢀ : ꢀOBut)2[( ꢀС5Me5)Ce( ꢀOBut)]2}
1
1
5
2
5
1
{( ꢀС5Me5)La[ ꢀCH(TMS)2]2}
5
1
[Li(dme)3][( ꢀС5H4Me)La( ꢀNPh2)3]
1.397
Compounds LnCp´X2(solv)m
5
[La( ꢀFlu)I2(py)3](PhMe)0.5
FIXFIC
FIXFEY
8
8
7
7
7
8
8
8
7
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
8
1.309, 1.294
1.293
1.278
1.277
1.275, 1.274
1.273
19
19
20
21
20
3
22
23
24
25
26
27
26
28
26
3
29
30
31
32
33
34
35
36
37
34
5
[Nd( ꢀFlu)I2(py)3](thf)
[Tm( ꢀC5HPri4)Cl2(dme)]
SEWWAT
IMOFAR
SEWVIA
IFUHEX
HOJWIM
VAGGEP
UHIDIY
OLOYET
MALYII
BOBWAQ
MALYAA
FEYWOV
MALXON
IFUHOH
BIQVOM
YEFVUA
WIPLOW
VEBKAO
QUCZAP
QUHQOZ
YAGHUJ01
IWUJOZ
WEWZED
QUHQIT
5
5
[Tm{ ꢀ1,3ꢀBut2ꢀ2ꢀ[OTmI2(thf)3]C5H2}I2(thf)2]
5
[Yb( ꢀ1,2,4ꢀBut3C5H2)Cl2(thf)2]
5
[Lu( ꢀ1,3ꢀPh2C5H3)Cl2(thf)3]
5
[Yb( ꢀB10C2H11—SiMe2—C5H4)Cl2(thf)3]
1.269
1.269
1.267
1.257
1.252
1.247
1.243
5
[Nd( ꢀB10C2H11—SiMe2—C5H4)Cl2(thf)3]
5
[Yb( ꢀC5HPri4)Cl2(dme)]
5
[La{ ꢀ1,2,4ꢀ(TMS)3C5H2}I2(py)3]
5
[La( ꢀBut—C5H4)I2(py)3]
5
[Er( ꢀC5H5)Cl2(thf)3]
5
[Ce( ꢀButC5H4)I2(py)3]
5
[Ce( ꢀC5Me5)I2(thf)3]
1.240, 1.233
1.238
5
[Nd( ꢀButC5H4)I2(py)3]
5
[Lu( ꢀC5H5)Cl2(thf)3]
1.238
1.236
1.235
1.232
1.227
1.221
1.220
1.216
5
[Sm{ ꢀ(2ꢀPriꢀ5ꢀMe—C6H9)—C5H4}I2(thf)3]
5
[Ho( ꢀC5H5)Cl2(thf)3]
5
[Nd( ꢀC5Me5)I2(py)3](PhMe)
5
[Lu( ꢀC5H5)(OTf)2(thf)3]
5
[Yb( ꢀMe—C5H4)(NCS)2(thf)3]
5
1
1
[La{ : : ꢀ1,3ꢀ(NMe2)2—C5H3}I2(thf)]
5
[Gd( ꢀC5H5)Cl2(thf)3]
5
[Tm( ꢀC5H5)I2(thf)3]
1.213
1.213
1.211
5
[Y( ꢀC5H5)Cl2(thf)3]
5
1
1
[La{ : : ꢀ1,2ꢀ(NMe2)2—C5H3}I2(thf)](thf)0.5
Compounds with minimum RCp
5
8
{( ꢀС5Me 4H)Yb( ꢀС8H8)}
ABIFIA
VAPZIV
8
8
9
9
9
9
8
8
9
1.120
1.117
1.116
38
39
40
41
40
40
42
43
44
5
8
{( ꢀС5Me5)Lu( ꢀС8H8)}
2
1
5
2
[Na(thf)6]{[Na(thf)4]( ꢀ : ꢀNO3)2[( ꢀС5Me5)Nd( ꢀNO3)2]2} PAGNAN
2
5
[( ꢀС5Me5)Tm(NCCH31)6]I2
SELMEC
PAGNER
PAGNIV
LAWREG
YEZNAS
NICHOW
1.113—1.114
1.106
2
5
2
[К(18ꢀcrownꢀ6)]( ꢀ : ꢀNO3)2[( ꢀС5Me5)Nd( ꢀNO3)]
2
2
1
2
2
5
{[Na(thf)2]( ꢀ : ꢀNO3)2( ꢀ : ꢀNO3)[( ꢀС5Me5)Nd]}
1.106
1.095
1.088
2
2
5
8
{( ꢀС5Me4H)Lu( ꢀС8H8)}
5
8
{( ꢀС5Me4Et)Lu( ꢀС8H8)}
5
{( ꢀС5H5)12( ꢀCl)24Sm12
}
1.079—1.094
3
* Fragments with C.N. 6.
hindrance (see Table 5). However, the RCp value poorly
correlated with the type of halide ligands X, ꢀdonor
ligands «solv», and electronic effects of the substituents in
the cyclopentadienyl ring.
RCp values for complexes 1 (1.266 Å) and 2 (1.264,
1.272 Å) lie in the range, which is inherent for
LnCp´X2(solv)m, closer to the maximum values due to
steric hindrance of diꢀ and triphenylcyclopentadienyl

Polyphenylcyclopentadienyl complexes
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 9, September, 2012
1731
Yb, 25.70; Cl, 10.60. C29H37Cl2YbO3. Calculated (%): Yb, 25.54;
Cl, 10.46.
ligands. Because of the presence of the bulky triphenyl
cyclopentadienyl ligand, RCp values are higher for the comꢀ
plex 5 (1.233, 1.224 and 1.231 Å), than for analogous
tetranuclear complexes [(С5H9—C5H4)3Er4Cl7O(thf)3]
(1.181, 1.182 and 1.189 Å), [(СH3—C5H4)3Yb4Cl7O(thf)3]
(1.194, 1.179 and 1.195 Å)8.
In the present work polyphenylsubstituted monocyꢀ
clopentadienyl dichloride complexes Yb(1,3ꢀPh2C5H3)ꢀ
Cl2(thf)3, Y(1,2,4ꢀPh3C5H2)Cl2(thf)3, Lu(1,2,4ꢀPh3ꢀ
C5H2)Cl2(thf)3 and La(Ph4C5H)Cl2(thf)3 have been synꢀ
thesized. The presence of phenyl substituents in the cycloꢀ
pentadienyl ligand decreases the tendency of LnCp´X2
complexes to metathesis and facilitates their isolation, preꢀ
venting formation of bisꢀ and trisꢀcyclopentadienyl derivꢀ
atives.
We have compared main structural parameters of
monocyclopentadienyl complexes of yttrium and lanꢀ
thanides using the CSD data. Intermediate values of RCp
(the difference between the length of Ln—Cpcentroid and
ionic radii of Ln3+) among all considered monocyclopenꢀ
tadienyl yttrium and lanthanide(III) complexes have been
observed for complexes Ln(PhnC5H5–n)Cl2(thf)3 (n = 2—3).
This phenomenon is observed despite of their apparent
high steric hindrance due to the presence of several phenyl
substituents in the cyclopentadienyl ring.
Dichloro 1,2,4ꢀtriphenylcyclopentadienide tris(tetrahydroꢀ
furanate) yttrium, Y(Ph3C5H2)Cl2(thf)3 (2). Complex 2 was obꢀ
tained as described for 1 starting from 0.884 g (3 mmol) 1,2,4ꢀ
triphenylcyclopentaꢀ1,3ꢀdiene, 0.25 g (10 mmol) of sodium hyꢀ
dride and 1.247 g (2.94 mmol) of YCl3(thf)3. Obtained 1.327 g
(2.05 mmol, 70%) as colorless microcrystalline product. Found (%):
Y, 13.72; Cl, 10.90. C35H41Cl2O3Y. Calculated (%): Y, 13.28;
Cl, 10.59. 1H NMR (500 МHz, THFꢀd8, ): 6.85—6.93 (m, 1 H);
6.94—7.26 (m, 12 Н); 7.28—7.42 (m, 4 Н).
The difference between the composition of the complex 2
found by Xꢀray structure analysis (Y(C5H2Ph3)Cl2(thf)3.5) and
from chemical analysis (Y(C5H2Ph3)Cl2(thf)3) can be explained
by the easy loss of the nonꢀcoordinated THF molecule upon
prolonged drying of the complex under vacuum.
Dichloro 1,2,4ꢀtriphenylcyclopentadienide tris(tetrahydroꢀ
furanate) lutetium, Lu(Ph3C5H2)Cl2(thf)3 (3). Complex 3 was
obtained as described for the complex 1 starting from 1.107 g
(3.76 mmol) 1,2,4ꢀtriphenylcyclopentaꢀ1,3ꢀdiene, 0.265 g
(11 mmol) sodium hydride and 1.833 g (3.69 mmol) LuCl3(thf)3.
Obtained 1.205 g (1.61 mmol, 44%) as colorless microcrystals
Lu(1,2,4ꢀPh3C5H2)Cl2(thf)3. Found (%): Lu, 23.40; Cl, 9.56.
Calculated (%): Lu, 23.16; Cl, 9.38. 1H NMR (500 МHz,
THFꢀd8, ): 6.84—6.86 (m, 1 Н); 6.90—7.22 (m, 12 Н);
7.28—7.35 (m, 4 Н).
Dichloro 1,2,3,4ꢀtetraphenylcyclopentadienide tris(tetraꢀ
hydrofuranate) lanthanum, La(Ph4C5H)Cl2(thf)3 (4). Complex 4
was synthesized as described for the complex 1 starting from
1.537 g (4.15 mmol) 1,2,3,4ꢀtetraphenylcyclopentadiene, 0.293 g
(12 mmol) of sodium hydride and 1.469 g (4.07 mmol) of
LaCl3(thf)2. Obtained 2.529 g (3.27 mmol, 80%) of colorless
Lа(Ph4C5H)Cl2(thf)3. Found (%): Lа, 17.94; Cl, 9.16. Calculatꢀ
Experimental
All synthetic operations and sample preparations for analysis
were carried out in sealed glass Schlenkꢀtype evacuated vessels.
Solvents were purified before earlier45. LnCl3(thf)3 were obtained
by hot THF extraction of anhydrous trichlorides of yttrium and
lanthanides, prepared by dehydration of corresponding hyꢀ
drates46. Diphenylcyclopentadiene3, 1,2,4ꢀtriphenylcyclopenꢀ
taꢀ1,3ꢀdiene47—49 and 1,2,3,4ꢀtetraphenylcyclopentaꢀ1,3ꢀdiꢀ
ene50,51 were synthesized as described in literature. Polyphenylꢀ
cyclopentadiens were purified by recrystallization from EtOH,
followed by sublimation under vacuum. Sodium polyphenylꢀ
cyclopentadienides were obtained by reaction of corresponding
polyphenylcyclopentadiens with excess of sodium hydride in
THF under reflux.
1H NMR spectra were recorded on Bruker DRXꢀ500 and
Bruker WMꢀ250 NMR spectrometers. Lanthanide content was
determined by direct complexometric titration in the presence
of Xylenol Orange indicator. Chlorine content was determined
by potentiometric titration with silver nitrate.
Dichloro 1,3ꢀdiphenylcyclopentadienide tris(tetrahydrofuranꢀ
ate) ytterbium, Yb(C5H3Ph2)Cl2(thf)3 (1). To a stirred solution
of sodium diphenylcyclopentadienide obtained from 0.676 g
(3.1 mmol) of diphenylcyclopentadiene and 0.282 g (11.7 mmol)
of sodium hydride in 50 mL of THF, 1.662 g (3.0 mmol) of
YbCl3(thf)3 was added. The mixture was stirred for 24 h.
The product was extracted with THF (3×50 mL), the mixture
was concentrated and the residue was extracted with toluene
(3×50 mL), the extract was evaporated, and the residue was reꢀ
crystallyzed from THF and dried under vacuum. Obtained 1.090 g
(1.62 mmol, 54%) of lightꢀviolet microcrystals. Found (%):
1
ed (%): Lа, 17.46; Cl, 8.91. H NMR (250 MHz, THFꢀd8, ):
7.0—7.8 (m).
Xꢀray structure analysis of complexes 1, 2 and 5. Crystalline
samples of the complexes for Xꢀray analysis were obtained from
THF (1 and 2) or THF—toluene mixture (2). Single crystals of 5
were obtained by slow diffusion of pentane into the THF soluꢀ
tion of 3 (pentane solution of 3, 3 : 1 V/V). Samples of 1, 2 and 5
were prepared as described earlier. The diffraction data were
collected using Smart 1000 CCD and Smart APEX II CCD
diffractometers ((MoꢀK) 0.71072 Å). Crystallographic data
and main refinement parameters for complexes 1, 2 and 5 are
presented in the Table 1. Multiple attempts to obtain good Xꢀray
quality single crystals of 2 under different conditions failed. Analꢀ
ysis of the reciprocal space showed that all selected crystals had
multiple components. Therefore, further refinement of 2 was
carried out using the intensity statistics for two main domains
(HKLF 5, BASF = 0.25). For complexes 1, 2 and 5 the data
were processed applying semiꢀempirical absorption corrections
based on intensities of equivalent reflections using the program
SADABS. The structures were solved by direct methods and
refined by fullꢀmatrix least squares anisotropically (for hydrogen
atoms — isotropically) against F2 using the SHELXTLꢀ97 proꢀ
gram package. All hydrogen atoms were placed in ideal geoꢀ
metrical positions and refined as riding atoms.
The work was accomplished with financial support
from the Russian Foundation for Fundamental Research
(grants 11ꢀ03ꢀ00043 and 10ꢀ03ꢀ00953).

1732
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 9, September, 2012
Roitershtein et al.
29. W.ꢀP. Leung, F.ꢀQ. Song, F. Xue, Z.ꢀY. Zhang, T. C. W.
Mak, J. Organomet. Chem., 1999, 582, 292.
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Received March 27, 2012;
in revised form July 3, 2012