Organometallic compounds of the lanthanides. 158.1 Alkenyl-functionalized cyclopentadienyl complexes of yttrium, samarium, and lutetium and their hydroboration

Article abstract of DOI:10.1021/om020654b

YCl₃, SmCl₃, and LuCl₃ react with (tetramethylvinylcyclopentadienyl)lithium (1a), yielding (CH₂=CHC₅Me₄)₂ Ln(μ-Cl)₂Li(Et₂O)₂ (Ln = Y (2a), Sm (2b

Full text of DOI:10.1021/om020654b

118
Organometallics 2003, 22, 118-128
Or ga n om eta llic Com p ou n d s of th e La n th a n id es. 158.1
Alk en yl-F u n ction a lized Cyclop en ta d ien yl Com p lexes of
Yttr iu m , Sa m a r iu m , a n d Lu tetiu m a n d Th eir
Hyd r obor a tion
Herbert Schumann,* Alexander Heim, J o¨rg Demtschuk, and Stefan H. Mu¨hle
Institut fu¨r Chemie der Technischen Universita¨t Berlin, Strasse des 17. J uni 135,
10623 Berlin, Germany
Received August 13, 2002
YCl3, SmCl3, and LuCl3 react with (tetramethylvinylcyclopentadienyl)lithium (1a ), yielding
(CH2dCHC5Me4)2Ln(µ-Cl)2Li(Et2O)2 (Ln ) Y (2a ), Sm (2b), Lu (2c)). LuCl3 and the analogous
potassium salt 1b form oligomeric [(CH2dCHC5Me4)2Lu(µ3-Cl)2K(THF)]n (3). Methylation
of the yttrium complex 2a with MeLi gives (CH2dCHC5Me4)2Y(µ-CH3)2Li(THF) (4). Hy-
droboration of the complexes 2a -c with 9-BBN results in the formation of (C8H14BCH2-
CH2C5Me4)2Ln(µ-Cl)2Li(THF)2 (Ln ) Y (5a ), Sm (5b), Lu (5c)). The reaction of YCl3 with 2
equiv of K[C5H4CHdC6H10] (6) or K[C5H4CHdCMe2] (10) affords the dimeric complexes
[(C6H10dCHC5H4)2Y(µ-Cl)]2 (7) and [(Me2CdCHC5H4)2Y(µ-Cl)]2 (11), whereas SmCl3 reacts
with 2 equiv of 6 or 10, yielding the tris(cyclopentadienyl) derivatives (C6H10dCHC5H4)3-
Sm(THF) (9) and (Me2CdCHC5H4)3Sm(THF) (13), respectively. Methylation of 7 with MeLi
yields unstable [(C6H10dCHC5H4)2Y(µ-CH3)]2 (7a ). SmI2 and 6 react with formation of (C6H10d
CHC5H4)2Sm(THF)2 (8). Hydrolysis during crystallization of 11 caused by some water in
the solvent leads to decomposition, forming the oxygen-bridged complex [(Me2CdCHC5H4)2Y-
(Et2O)]2(µ-O) (12). The ansa-lanthanidocene chloride [H2CdC(CH2C5H4)2]LuCl(THF) (15) was
prepared from LuCl3 and the new ligand K2[H2CdC(CH2C5H4)2] (14). The structures of 2a ,
3, 5b, 7, and 12 were determined by single-crystal X-ray diffraction.
In tr od u ction
olefinic double bond is not able to stabilize the metal
center by intramolecular coordination. In this context
and for the following reasons, we started to synthesize
and to investigate lanthanide complexes with vinyl-
substituted cyclopentadienyl ligands. First, the vinyl
side chain is shorter than a dangling ω-alkenyl group
and should therefore promote the crystallization of such
complexes. Second, vinyl side chains should be capable
of copolymerizing metallocenes with other monomers8
suitable for polymerization, thus leading to immobilized
olefin polymerization catalysts containing lanthanide
Organolanthanide chemistry has produced an im-
pressive number of highly active homogeneous catalysts.
Various alkene and alkyne transformations are ef-
fectively catalyzed by lanthanidocenes.2 Among them,
the most active catalysts are organolanthanide hydrides
of the type [(C5Me5)2Ln(µ-H)]2 which can be generated
from the respective halide precursors [(C5Me5)2Ln(µ-
Cl)]2. More than 90% of the known organolanthanide
complexes contain cyclopentadienyl groups as the most
powerful ligand in this field, and substantial research
activities are focused on the modification of the coordi-
nation sphere of the lanthanide metals by variation of
the substituents at the cyclopentadienyl ligands in order
to achieve better catalytic properties.3
(5) (a) J utzi, P.; Dahlhaus, J .; Kristen, M. O. J . Organomet. Chem.
1993, 450, C1. (b) Herrmann, W. A.; Anwander, R.; Munck, F. C.;
Scherer, W. Chem. Ber. 1993, 126, 331. (c) Anwander, R.; Herrmann,
W. A.; Scherer, W.; Munck, F. C. J . Organomet. Chem. 1993, 462, 163.
(d) Schumann, H.; Erbstein, F.; Herrmann, K.; Demtschuk, J .; We-
imann, R. J . Organomet. Chem. 1998, 562, 255. (e) Schumann, H.;
Rosenthal, E. C. E.; Demtschuk, J .; Molander, G. A. Organometallics
1998, 17, 5324. (f) Schumann, H.; Erbstein, F.; Karasiak, D. F.;
Fedushkin, I. L.; Demtschuk, J .; Girgsdies, F. Z. Anorg. Allg. Chem.
1999, 625, 781. (g) Schumann, H.; Erbstein, F.; Demtschuk, J .;
Weimann, R. Z. Anorg. Allg. Chem. 1999, 625, 1457. (h) Schumann,
H.; Rosenthal, E. C. E.; Demtschuk, J .; Mu¨hle, S. Z. Anorg. Allg. Chem.
2000, 626, 2161. (i) Fedushkin, I. L.; Dechert, S.; Schumann, H.
Organometallics 2000, 19, 4066.
(6) (a) Deng, D.; Li, B.; Qian, C. Polyhedron 1990, 12, 1453. (b) Deng,
D.; Qian, C.; Wu, G.; Zheng, P. J . Chem. Soc., Chem. Commun. 1990,
880. (c) Qian, C.; Zhu, D.; Li, D. J . Organomet. Chem. 1992, 430, 175.
(d) Laske, D. A.; Duchateau, R.; Teuben, J . H.; Spek, A. L. J .
Organomet. Chem. 1993, 462, 149. (e) Qian, C.; Zou, G.; Sun, J . J .
Organomet. Chem. 1998, 566, 21.
Recently, we reported on the properties of organolan-
thanide complexes with ω-alkenyl-substituted cyclopen-
tadienyl ligands.4 Compared to complexes with cyclo-
pentadienyls containing strong donor atoms such as
nitrogen, oxygen, and sulfur in their side chains,5-7 the
* To whom correspondence should be addressed. E-mail:
schumann@chem.tu-berlin.de.
(1) Part 157: Schumann, H.; Freckmann, D. M. M.; Dechert, S. Z.
Anorg. Allg. Chem. 2002, 628, 2422.
(2) (a) Applied Homogeneous Catalysis with Organometallic Com-
pounds; Corniels, B., Herrmann, W. A., Eds.; VCH: Weinheim,
Germany, 1996. (b) Metallocenes; Togni, A., Halterman, R. L., Eds.;
Wiley-VCH: Weinheim, Germany, 1998.
(3) Edelmann, F. T. Top. Curr. Chem. 1996, 179, 247.
(4) Schumann, H.; Heim, A.; Demtschuk, J .; Mu¨hle, S. H. Organo-
metallics 2002, 21, 3323.
(7) Schumann, H.; Hermann, K.; Demtschuk, J .; Mu¨hle, S. Z. Anorg.
Allg. Chem. 1999, 625, 1107.
(8) Pfeifer, B.; Milius, W.; Alt, H. G. J . Organomet. Chem. 1998,
553, 205.
10.1021/om020654b CCC: $25.00 © 2003 American Chemical Society
Publication on Web 12/02/2002

Organometallic Compounds of the Lanthanides
Organometallics, Vol. 22, No. 1, 2003 119
clopentadiene and 5-ethylidene-1,2,3,4-tetramethyl-1,3-cyclo-
pentadiene12 (5.63 g, 38 mmol) in tetrahydrofuran (150 mL)
was added K[N(SiMe3)2] (7.58 g, 38 mmol) at -78 °C. The
reaction mixture was stirred for 12 h at room temperature.
After removal of the solvent under vacuum (10-2 mbar), the
remaining beige solid was washed several times with hexane,
leaving 5.43 g (77%) of a pyrophoric gray-white powder of 1b;
mp 241 °C. 1H NMR (pyridine-d5, 200 MHz): δ 7.26 (dd, 3J trans
metals. Third, the vinyl substituent can be used for
a further functionalization of the cyclopentadienyl
ligand: for example, by the introduction of a borane
group via hydroboration.9 Following the concept of
zwitterionic metallocenes,10 such a second Lewis acidic
borane moiety could cause a huge impact on the
catalytic properties of the lanthanidocenes. Further-
more, we wanted to use the tool of hydroboration to link
two vinyl side chains, thus generating a borane-bridged
cyclopentadienyl ligand system. So far, only borane-
bridged ansa ligands are known in which the boron
atom is directly bonded to two cyclopentadienyl units.11
Here we report the synthesis of a number of yttrium-
(III), samarium(II/III), and lutetium(III) complexes
containing cyclopentadienyl ligands with differently
substituted vinyl side chains and one bridging allylic
ligand system. The successful hydroboration of the bis-
(tetramethylvinylcyclopentadienyl)lanthanide chlorides
(Ln ) Y, Sm, Lu) demonstrates the potential of (vinyl-
cyclopentadienyl)lanthanide complexes for further func-
tionalization.
3
3
) 17.5 Hz, J cis ) 10.6 Hz, 1 H, CHd), 5.10 (dd, J trans ) 17.5
3
Hz, 2J ) 2.7 Hz, 1 H, dCH2), 4.64 (dd, J cis ) 10.6 Hz, 2J )
2.6 Hz, 1 H, dCH2), 2.42 (s, 6 H, CH3), 2.25 (s, 6 H, CH3). 13C-
{1H} NMR (pyridine-d5, 50.32 MHz): δ 135.17 (-CHd), 112.67
(C-C2H3), 111.02 (C-CH3), 110.31 (C-CH3), 93.34 (dCH2),
12.82 (CH3), 11.40 (CH3). MS (296 °C; m/z (%)): 148 (68)
[C11H16]+, 147 (21) [C11H15]+, 134 (12), 133 (100), 131 (16), 119
(13), 117 (13), 115 (11), 105 (27), 91 (23), 41 (15). Anal. Calcd
for C11H15K (mol wt 186.34): C, 70.90; H, 8.11. Found: C,
70.60; H, 7.85.
Bis(d ieth yl eth er )lith iu m Bis(µ-Ch lor o)bis(tetr a m eth -
ylvin ylcyclop en ta d ien yl)yttr iu m (2a ). To a suspension of
YCl3 (1.50 g, 7.7 mmol) in THF (80 mL) was added Li[C5Me4-
CHdCH2] (1a ; 2.37 g, 15.4 mmol) at room temperature, and
the reaction mixture was stirred for 6 h. After removal of the
solvent under vacuum (10-2 mbar), the residue was extracted
with diethyl ether (70 mL). The resulting ether solution was
concentrated and cooled to 0 °C, yielding 2.1 g (45%) of pale
yellow crystals of 2a ; mp 97 °C dec. 1H NMR (benzene-d6, 200
MHz): δ 6.92 (dd, 3J trans ) 18.0 Hz, 3J cis ) 11.6 Hz, 2 H, -CHd
Exp er im en ta l Section
All operations involving organometallic compounds were
carried out under an inert atmosphere of nitrogen or argon
using standard Schlenk techniques in dry, oxygen-free sol-
vents. Melting points were measured in sealed capillaries with
a Bu¨chi 510 melting point determination apparatus and are
uncorrected. The NMR spectra were recorded on a Bruker ARX
200 (1H, 200 MHz; 13C, 50.32 MHz) or ARX 400 (1H, 400 MHz;
13C, 100.64 MHz) spectrometer at 298 K. Chemical shifts are
reported in ppm relative to the 1H and 13C residue of the
deuterated solvents. Mass spectra (EI, 70 eV) were obtained
by using a Varian MAT 311 A/AMD instrument. Only char-
acteristic fragments containing the isotopes of the highest
abundance are listed. Relative intensities are given in paren-
theses. Elemental analyses were performed on a Perkin-Elmer
Series II CHNS/O analyzer 2400. (Tetramethylvinylcyclopen-
tadienyl)lithium (1a ),12 (2,4-cyclopentadien-1-ylidenemethyl)-
cyclohexane,13 5-isobutylidenecyclopentadiene,13 and SmI2-
3
), 5.38 (dd, J trans ) 18.0 Hz, 2J ) 2.2 Hz, 2 H, dCH2), 5.04
3
2
3
(dd, J cis ) 11.6 Hz, J ) 2.2 Hz, 2 H, dCH2), 3.19 (q, J ) 7.0
Hz, 8 H, CH2(Et2O), 2.24 (s, 12 H, CH3), 2.08 (s, 12 H, CH3),
0.99 (t, 3J ) 7.0 Hz, 12 H, CH3(Et2O)). 13C{1H} NMR (benzene-
d6, 50.32 MHz): δ 133.59 (-CHd), 120.49 (d, 1J (89Y,13C) ) 1.3
Hz, C-CH3), 119.59 (d, J (89Y,13C) ) 1.3 Hz, C-CH3), 117.04
1
(d, 1J (89Y,13C) ) 1.4 Hz, C-C2H3), 107.59 (dCH2), 65.83 (CH2,
Et2O), 14.86 (CH3, Et2O), 12.82 (CH3), 11.60 (CH3). MS (313
°C; m/z (%)): 420 (54) [M - LiClC8H20]+, 418 (71) [M -
LiClC8H22]+, 403 (100) [C21H26YCl]+, 382 (10) [C22H28Y]+, 273
(76) [C11H15YCl]+, 271 (92) [C11H13YCl]+, 148 (11) [C11H16]+,
135 (73) [C10H15]+. Anal. Calcd for C30H50Cl2LiO2Y (mol wt
609.48): C, 59.12; H, 8.27. Found: C, 58.90; H, 7.31 (Calcd
for C22H30Cl2LiY(OC4H10) after losing one molecule of diethyl
ether under vacuum: C, 58.33; H, 7.53).
14
(THF)2 were prepared according to published procedures.
Bis(d ieth yl eth er )lith iu m Bis(µ-Ch lor o)bis(tetr a m eth -
ylvin ylcyclop en ta d ien yl)sa m a r iu m (2b). In analogy to the
preparation of 2a , SmCl3 (1.43 g, 5.6 mmol) in THF (80 mL)
was reacted with Li[C5Me4CHdCH2] (1a ; 1.72 g, 11.14 mmol)
to provide 2.10 g (56%) of orange crystals of 2b; mp 112 °C
dec. 1H NMR (benzene-d6, 200 MHz): δ 7.03 (ddbr, 3J cis ) 11.3
Anhydrous YCl3, SmCl3, and LuCl3 were prepared from the
pure oxides by reaction with NH4Cl followed by Soxhlet
extraction of the trichlorides formed with THF.15
(Tetr a m eth ylvin ylcyclop en ta d ien yl)p ota ssiu m (1b).
To a solution of the isomeric mixture of tetramethylvinylcy-
3
3
Hz, J trans ) 17.6 Hz, 2 H, -CHd), 5.16 (dbr, J trans ) 17.6 Hz,
3
2 H, dCH2), 4.84 (dbr, J cis ) 11.3 Hz, 2 H, dCH2), 3.30 (q, 8
(9) Erker, G.; Aul, R. Chem. Ber. 1991, 124, 1301.
(10) Piers, W. E. Chem. Eur. J . 1998, 4, 13.
H, CH2, Et2O), 1.71 (sbr, 12 H, CH3), 1.12 (s, 12 H, CH3), 1.03
(t, 12 H, CH3, Et2O). 13C{1H} NMR (benzene-d6, 50.32 MHz):
δ 141.09 (-CHd), 120.96 (C-CH3), 117.74 (C-CH3), 116.75
(C-C2H3), 103.99 (dCH2), 65.79 (CH2, Et2O), 17.55 (CH3),
17.48 (CH3), 14.90 (CH3, Et2O). MS (152Sm, 403 °C; m/z (%)):
481 (2) [M - LiClC8H20]+, 445 (2) [M - LiCl2C8H22]+, 335 (4)
[C11H15SmCl]+, 299 (3) [C11H15Sm]+, 148 (29) [C11H16]+, 135
(73) [C10H15]+. Anal. Calcd for C30H50Cl2LiO2Sm (mol wt
670.93): C, 53.71; H, 7.51. Found: C, 50.43; H, 5.92 (Calcd
for C22H30Cl2LiSm after losing two molecules of diethyl ether
under vacuum: C, 50.55; H, 5.79).
(11) (a) Reetz, M. T.; Bru¨mmer, H.; Kessler, M.; Kuhnigk, J . Chimia
1995, 49, 501. (b) Bochmann, M.; Lancaster, S. J .; Robinson, O. B. J .
Chem. Soc., Chem. Commun. 1995, 2081. (c) Duchateau, R.; Lancaster,
S. J .; Thornton-Pett, M.; Bochmann, M. Organometallics 1997, 16,
4995. (d) Lancaster, S. J .; Thornton-Pett, M.; Dawson, D. M.; Boch-
mann, M. Organometallics 1998, 17, 3829. (e) Ruwe, J .; Erker, G.;
Fro¨hlich, R. Angew. Chem. 1996, 108, 108; Angew. Chem., Int. Ed.
Engl. 1996, 35, 80. (f) Larkin, S. A.; Golden, J . T.; Shapiro, P. J .; Yap,
G. P. A.; Foo, D. M. J .; Rheingold, A. L. Organometallics 1996, 15,
287. (g) Rufanov, K. A.; Kotov, V. V.; Kazennova, N. B.; Lemenovskii,
D. A.; Avtomonov, E. V.; Lorberth, J . J . Organomet. Chem. 1996, 525,
287. (h) Stelck, D. S.; Shapiro, P. J .; Basickes, N.; Rheingold, A. L.
Organometallics 1997, 16, 4546. (i) Rufanov, K. A.; Avtomonov, E. V.;
Kazennova, N. B.; Kotov, V. V.; Khvorost, A.; Lemenovskii, D. A.;
Lorberth, J . J . Organomet. Chem. 1997, 536, 361. (j) Reetz, M. T.;
Willuhn, M.; Psiorz, C.; Goddard, R. Chem. Commun. 1999, 1105.
(12) (a) Macomber, D. W.; Spink, W. C.; Rausch, M. D. J . Organomet.
Chem. 1983, 250, 311. (b) Bensley, D. M.; Mintz, E. A. J . Organomet.
Chem. 1988, 250, 311.
Bis(d ieth yl eth er )lith iu m Bis(µ-Ch lor o)bis(tetr a m eth -
ylvin ylcyclop en ta d ien yl)lu tetiu m (2c). In analogy to the
preparation of 2a , LuCl3(THF)3 (2.23 g, 4.5 mmol) in THF (80
mL) was reacted with Li[C5Me4CHdCH2] (1a ; 1.38 g, 8.96
mmol) to provide 1.88 g (60%) of pale yellow crystals of 2c;
1
(13) Stone, K. J .; Little, R. D. J . Org. Chem. 1984, 49, 1849.
(14) Watson, P. L.; Tulip, T. H.; Williams, I. Organometallics 1990,
9, 1999.
(15) Brauer, G. Handbuch der Pra¨parativen Anorganischen Chemie;
F. Enke Verlag: Stuttgart, Germany, 1962; Vol. 2, p 1002.
mp 117 °C dec. H NMR (benzene-d6, 200 MHz): δ 6.93 (dd,
3
3
3J trans ) 18.0 Hz, J cis ) 11.6 Hz, 2 H, -CHd), 5.35 (dd, J trans
4
3
) 18.0 Hz, J ) 2.2 Hz, 2 H, dCH2), 5.02 (dd, J cis ) 11.6 Hz,
4J ) 2.2 Hz, 2 H, dCH2), 3.19 (q, 3J ) 7.0 Hz, 8 H, CH2(Et2O),

120 Organometallics, Vol. 22, No. 1, 2003
Schumann et al.
3
2.23 (s, 12 H, CH3), 2.09 (s, 12 H, CH3), 0.99 (t, J ) 7.0 Hz,
12 H, CH3(Et2O)). 13C{1H} NMR (benzene-d6, 50.32 MHz): δ
134.04 (-CHd), 119.80 (C-CH3), 119.02 (C-CH3), 116.76 (C-
C2H3), 107.28 (dCH2), 65.82 (CH2, Et2O), 14.88 (CH3, Et2O),
12.99 (CH3), 11.78 (CH3). MS (175Lu, 334 °C; m/z (%)): 504 (66)
[M - LiClC8H20]+, 489 (56) [C21H27LuCl]+, 469 (4) [C22H30Lu]+,
357 (100) [C11H15LuCl]+, 148 (84) [C11H16]+. Anal. Calcd for
2THF)]+, 393 (4) [M - C19H30B]+, 270 (25) [C19H31B]+, 256 (6)
[C18H29B]+, 230 (4), 194 (4), 162 (10), 148 (18) [C11H18]+, 135
(100) [C10H15]+, 122 (42) [9-BBN]+, 108 (11). Anal. Calcd for
C
46H76B2YCl2LiO2 (mol wt 849.48): C, 65.04; H, 9.02. Found:
C, 64.02; H, 8.22 (Calcd for C38H60B2YCl2Li after loss of two
molecules of THF under vacuum: C, 64.72; H, 8.57).
Bis(tetr a h yd r ofu r a n )lith iu m Bis(µ-Ch lor o)bis{(2-(9-
b o r a b ic y c lo [3.3.1]n o n -9-y l)e t h y l)t e t r a m e t h y lc y c lo -
p en ta d ien yl}sa m a r iu m (5b). In analogy to the preparation
of 5a , compound 2b (0.64 g, 0.95 mmol) dissolved in toluene
(30 mL) was reacted with 9-BBN (3.81 mL, 0.5 M in THF, 1.9
mmol) to provide 0.70 g (81%) of yellow crystals of 5b; mp 139
°C. 1H NMR (benzene-d6, 400 MHz): δ 3.95 (sbr, 8 H, THF),
1.94 (sbr, 4 H, CH2), 1.85-1.39 (m, 60 H, CH, CH2, CH3), 1.10
(sbr, 4 H, CH2). 13C{1H} NMR (benzene-d6, 100.64 MHz): δ
122.83 (C-C2H4-9-BBN), 117.74 (C-CH3), 115.01 (C-CH3),
68.70 (CH2, THF), 33.32 (CH2, 9-BBN), 31.44 (CH, 9-BBN),
26.78 (CH2), 26.52 (CH2), 27.11 (CH2, THF), 23.49 (CH2,
9-BBN), 18.27 (CH3), 18.10 (CH3). MS (152Sm, 234 °C; m/z
(%)): 725 (0.4) [M - (LiCl, 2THF)]+, 457 (0.6) [M - C19H30B]+,
336 (2) [M - C27H44B2]+, 270 (33) [C19H31B]+, 256 (21)
[C18H29B]+, 230 (22), 194 (7), 162 (9), 148 (13) [C11H16]+, 135
(100) [C10H15]+, 122 (82) [9-BBN]+, 107 (49), 94 (100), 79 (68),
67 (72), 53 (65), 41 (97). Anal. Calcd for C46H76B2SmCl2LiO2
(mol wt 910.94): C, 60.65; H, 8.41. Found: C, 59.87; H, 8.49.
Bis(tetr a h yd r ofu r a n )lith iu m Bis(µ-Ch lor o)bis{(2-(9-
b o r a b ic y c lo [3.3.1]n o n -9-y l)e t h y l)t e t r a m e t h y lc y c lo -
p en ta d ien yl}lu tetiu m (5c). In analogy to the preparation
of 5a , compound 2c (0.34 g, 0.48 mmol) dissolved in toluene
(30 mL) was reacted with 9-BBN (1.95 mL 0.5 M in THF, 0.96
mmol) to provide 0.39 g (87%) of pale yellow crystals of 5c;
mp 141 °C. 1H NMR (benzene-d6, 200 MHz): δ 3.52 (mbr, 8 H,
THF), 3.12-3.00 (m, 4 H, CH2), 2.34 (s, 12 H, CH3), 2.26 (s,
12 H, CH3), 2.00-1.65 (m, 32 H, CH, CH2), 1.34 (mbr, 8 H,
THF). 13C{1H} NMR (benzene-d6, 50.32 MHz): δ 124.07 (C-
C2H4-9BBN), 117.49 (C-CH3), 115.42 (C-CH3), 68.31 (CH2,
THF), 33.53 (CH2, 9-BBN), 31.62 (CH, 9-BBN), 30.53 (CH2),
25.41 (CH2, THF), 23.69 (CH2, 9-BBN), 21.67 (CH2), 12.25
(CH3), 12.11 (CH3). MS (175Lu, 217 °C; m/z (%)): 748 (0.8) [M
- (LiCl, 2THF)]+, 479 (2) [M - C19H30B]+, 358 (2) [M -
C
30H50Cl2LiLuO2 (mol wt 695.54): C, 51.81; H, 7.25. Found:
C, 50.28; H, 6.35 (Calcd for C22H30Cl2LiLu(OC4H10) after losing
one molecule diethyl ether under vacuum: C, 50.25; H, 6.49).
(Tetr a h yd r ofu r a n )p ota ssiu m Bis(µ-Ch lor o)bis(tetr a m -
eth ylvin ylcyclop en ta d ien yl)lu tetiu m (3). To a suspension
of LuCl3(THF)3 (3.31 g, 6.65 mmol) in THF (80 mL) was added
K[C5Me4CHdCH2] (1b; 2.47 g, 13.3 mmol) at room tempera-
ture, and the reaction mixture was stirred for 12 h. After
filtration and removal of the solvent under vacuum (10-2 mbar)
2.30 g (53%) of a pale yellow powder of 3 were obtained; mp
247 °C dec. 1H NMR (pyridine-d5, 200 MHz): δ 6.68 (dd, 3J trans
3
3
) 18.0 Hz, J cis ) 11.6 Hz, 2 H, -CHd), 5.17 (dbr, J trans
)
3
18.0 Hz, 2 H, dCH2), 5.04 (dbr, J cis ) 11.6 Hz, 2 H, dCH2),
3.65 (sbr, 4 H, CH2(THF)), 2.30-1.70 (m, 24 H, CH3), 1.61 (sbr,
4 H, CH2(THF)). 13C{1H} NMR (pyridine-d5, 50.32 MHz): δ
132.16 (-CHd), 121.16, 119.89, 118.28, 117.77, 117.58 (C-
CH3, C-C2H3), 109.21 (dCH2), 67.84 (CH2, THF), 25.82 (CH2,
THF), 13.86, 12.96, 12.52, 12.07, 11.74, 11.50 (CH3). MS
(
175Lu, 334 °C; m/z (%)): 504 (66) [M - KClC4H8]+, 489 (56)
[C21H27LuCl]+, 469 (4) [C22H30Lu]+, 357 (100) [C11H15LuCl]+,
148 (84) [C11H16]+. Anal. Calcd for C26H38Cl2KLuO (mol wt
651.56): C, 47.93; H, 5.88. Found: C, 47.63; H, 5.83.
(Tetr a h yd r ofu r a n )lith iu m Bis(µ-Meth yl)bis(tetr a m e-
th ylvin ylcyclop en ta d ien yl)yttr iu m (4). To a solution of
YCl3 (0.24 g, 1.21 mmol) in tetrahydrofuran (50 mL) was added
Li[C5Me4CHdCH2] (1a ; 0.37 g, 2.42 mmol), and the mixture
was refluxed for 2 h. After removal of the solvent under
vacuum (10-2 mbar), the residue was extracted with diethyl
ether (50 mL). The extract was cooled to -78 °C, followed by
slow addition of MeLi (1.5 M in diethyl ether, 0.81 mL, 1.21
mmol). After the reaction mixture was stirred for 12 h, it was
filtered and the solvent was removed from the filtrate under
vacuum (10-2 mbar). The remaining pale yellow powder was
extracted with hexane (40 mL). The extract was concentrated
and stored at -78 °C, yielding a few pale yellow crystals of 4,
which decompose immediately at room temperature. 1H NMR
C
27H44B2]+, 270 (29) [C19H31B]+, 256 (5) [C18H29B]+, 230 (4),
162 (11), 148 (20) [C11H16]+, 135 (100) [C10H15]+, 122 (45)
[9-BBN]+, 107 (17), 93 (28), 79 (24), 67 (18), 53 (22). Anal. Calcd
for C46H76B2LuCl2LiO2 (mol wt 935.54): C, 59.06; H, 8.19.
Found: C, 57.26; H, 7.72 (Calcd for C38H60B2LuCl2Li after
losing two molecules of THF under vacuum: C, 57.68; H, 7.64).
( ( C y c l o h e x y l i d e n e m e t h y l ) c y c l o p e n t a d i e n y l ) -
p ota ssiu m (6). To a solution of (2,4-cyclopentadien-1-ylidene-
methyl)cyclohexane (5.03 g, 31 mmol) in tetrahydrofuran (150
mL), precooled to -20 °C, was added K[N(SiMe3)2] (6.27 g, 31
mmol). The reaction mixture was stirred for 2 h at room
temperature. Then the solvent was removed under vacuum
(10-2 mbar), leaving a viscous brown oil, to which hexane (40
mL) was added. The mixture was stirred for 30 min, and then
the solvent was decanted and the remaining oily residue was
dried under vacuum. Again hexane (30 mL) was added. After
prolonged stirring 5.61 g (91%) of pyrophoric, gray-white,
powdery 6 precipitated; mp 205 °C. 1H NMR (pyridine-d5, 200
MHz): δ 6.51 (s, 1 H, CH), 6.36-6.32 (m, 2 H, CH), 6.30-6.26
(m, 2 H, CH), 2.90-2.80 (mbr, 2 H, CH2), 2.40-2.30 (mbr, 2 H,
CH2), 1.67-1.50 (mbr, 6 H, CH2). 13C{1H} NMR (pyridine-d5,
100.64 MHz): δ 125.29 (-Cd), 123.29 (CH), 119.07 (C-C7H11),
107.34 (CH, Cp), 106.10 (CH, Cp), 38.20 (CH2), 30.01 (CH2),
29.03 (CH2), 27.63 (CH2), 27.27 (CH2). MS (284 °C; m/z (%)):
198 (7) [M]+, 159 (30) [C12H15]+, 143 (5), 129 (21), 115 (22),
103 (5), 91 (37), 79 (25), 67 (14), 39 (100). Anal. Calcd for
3
(pyridine-d5, 200 MHz, -40 °C): δ 7.13 (dd, J trans ) 17.8 Hz,
3J cis ) 11.6 Hz, 2 H, -CHd), 5.36 (dd, J trans ) 17.8 Hz, J )
2.5 Hz, 2 H, dCH2), 5.04 (dd, 3J cis ) 11.6 Hz, 2J ) 2.5 Hz, 2 H,
dCH2), 3.67 (m, 4 H, THF), 2.44 (s, 12 H, CH3), 2.32 (s, 12 H,
3
2
CH3), 1.66 (m, 4 H, THF), -0.775 (d, J (89Y,1H) ) 2 Hz, 6 H,
2
CH3). 13C{1H} NMR (pyridine-d5, 50.32 MHz): δ 134.76
(-CHd), 115.65 (C-CH3), 113.90 (C-C2H3), 112.92 (C-CH3),
103.54 (dCH2), 67.52 (CH2, THF), 25.49 (CH2, THF), 18.17
(CH3), 17.18 (CH3), 12.88 (CH3), 11.91 (CH3).
Bis(tetr a h yd r ofu r a n )lith iu m Bis(µ-Ch lor o)bis{(2-(9-
b o r a b ic y c lo [3.3.1]n o n -9-y l)e t h y l)t e t r a m e t h y lc y c lo -
p en ta d ien yl}yttr iu m (5a ). To a solution of 2a (1.39 g, 2.28
mmol) in toluene (80 mL) was added 9-BBN (9.12 mL 0.5 M
in THF, 4.56 mmol) slowly at room temperature. After the
reaction mixture was stirred for 12 h, it was filtered. Removal
of the solvent from the filtrate under vacuum (10-2 mbar) left
a residue which was washed only once with pentane (10 mL)
and was then dissolved in hexane. Cooling of the hexane
solution to 0 °C caused precipitation of 1.33 g (69%) of colorless
1
crystals of 5a ; mp 128 °C. H NMR (benzene-d6, 200 MHz): δ
3.54 (mbr, 8 H, THF), 3.10-2.99 (m, 4 H, CH2), 2.34 (s, 12 H,
CH3), 2.25 (s, 12 H, CH3), 2.00-1.62 (m, 32 H, CH, CH2), 1.32
(mbr, 8 H, THF). 13C{1H} NMR (benzene-d6, 50.32 MHz): δ
124.81 (C-C2H4-9-BBN), 118.24 (d, 1J (89Y,13C) ) 1.2 Hz,
C-CH3), 116.28 (C-CH3), 68.36 (CH2, THF), 33.53 (CH2,
9-BBN), 31.70 (CH, 9-BBN), 30.55 (CH2), 25.36 (CH2, THF),
23.67 (CH2, 9-BBN), 23.57 (CH2, 9-BBN), 21.46 (CH2), 12.08
(CH3), 11.92 (CH3). MS (211 °C; m/z (%)): 662 (2) [M - (LiCl,
C
12H15K: (mol wt 198.35): C, 72.67; H, 7.62. Found: C, 73.31;
H, 8.12.
B i s ((c y c lo h e x y li d e n e m e t h y l)c y c lo p e n t a d i e n y l)-
yttr iu m Ch lor id e (7). To a suspension of YCl3 (0.78 g, 4
mmol) in THF (75 mL) was added K[C5H4CHdC6H10] (6; 1.59

Organometallic Compounds of the Lanthanides
Organometallics, Vol. 22, No. 1, 2003 121
g, 8 mmol) at room temperature, and the reaction mixture was
stirred for 12 h. After removal of the solvent under vacuum
(10-2 mbar), the residue was extracted with hexane (60 mL).
The resulting hexane extract was concentrated and cooled to
-25 °C, yielding 0.85 g (48%) of colorless crystals of 7; mp 92
°C. 1H NMR (benzene-d6, 200 MHz): δ 6.44-6.41 (m, 8 H, CH),
6.23-6.20 (m, 8 H, CH), 6.16 (s, 4 H, CH), 2.56-2.50 (m, 8 H,
CH2), 2.26-2.20 (m, 8 H, CH2), 1.67-1.42 (m, 24 H, CH2). 13C-
{1H} NMR (benzene-d6, 50.32 MHz): δ 141.06 (-Cd), 126.80
(d, 1J (89Y,13C) ) 1.1 Hz, C-C7H11), 116.90 (CH), 113.41 (d,
(pyridine-d5, 200 MHz): δ 6.51 (s, 1 H, CH), 6.28-6.21 (m, 4
H, CH), 2.03 (s, 3 H, CH3), 1.91 (s, 3 H, CH3). 13C{1H} NMR
(pyridine-d5, 50.32 MHz): δ 126.10 (-Cd), 123.12 (CH), 115.76
(C-C4H7), 107.01 (CH, Cp), 106.19 (CH, Cp), 27.52 (CH3), 20.09
(CH3). MS (197 °C; m/z (%)): 158 (0.4) [M]+, 120 (71) [C9H11]+,
105 (100), 91 (38), 77 (29), 65 (8), 51 (10), 39 (13). Anal. Calcd
for C9H11K (mol wt 158.28): C, 68.29; H, 7.00. Found: C, 68.46;
H, 6.57.
Bis(2-m e t h yl-1-p r op e n ylcyclop e n t a d ie n yl)yt t r iu m
Ch lor id e (11). In analogy to the preparation of 7, YCl3 (1.20
g, 6.14 mmol) suspended in THF (80 mL) was reacted with
K[C5H4CHdCMe2] (10; 1.94 g, 12.3 mmol). After removal of
the solvent under vacuum (10-2 mbar), the residue was
extracted with diethyl ether (60 mL). The clear solution was
decanted, the diethyl ether removed under vacuum (10-2
mbar), and the residue washed twice with pentane (2 × 10
mL), yielding 0.93 g (42%) of a beige powder of 11; mp 85 °C.
1H NMR (benzene-d6, 200 MHz): δ 6.41-6.39 (m, 8 H, CH),
6.21-6.17 (m, 8 H, CH), 6.19 (s, 4 H, CH), 1.87 (s, 6 H, CH3),
1.86 (s, 6 H, CH3), 1.79 (s, 6 H, CH3), 1.78 (s, 6 H, CH3). 13C-
{1H} NMR (benzene-d6, 50.32 MHz): δ 132.48 (-Cd), 127.23
(C-C4H7), 119.99 (CH), 113.38 (CH, Cp), 112.74 (CH, Cp),
27.31 (CH3), 20.09 (CH3). MS (169 °C; m/z (%)): 724 (1.5) [M]+,
607 (42) [C27H33Y2Cl2]+, 362 (1) [M(monomer)]+, 327 (100)
[C18H22Y]+, 273 (7) [C14H16Y]+, 243 (5) [C9H11YCl]+, 207 (9)
[C9H11Y]+, 160 (8), 120 (18) [C9H12]+, 105 (20). Anal. Calcd for
(C18H22YCl)2 (mol wt 725.46): C, 59.60; H, 6.11. Found: C,
59.24; H, 6.17.
1
1J (89Y,13C) ) 1.1 Hz, CH, Cp), 113.18 (d, J (89Y,13C) ) 1.0 Hz,
CH, Cp), 38.24 (CH2), 30.39 (CH2), 29.04 (CH2), 27.88 (CH2),
26.91 (CH2). MS (217 °C; m/z (%)): 886 (1) [M]+, 727 (42)
[C36H45Y2Cl2]+, 567 (1) [C24H30Y2Cl2]+, 443 (0.3) [M(mono-
mer)]+, 407 (100) [C24H30Y]+, 283 (4) [C12H15YCl]+, 247 (1)
[C12H14Y]+, 1600 (8) [C12H16]+. Anal. Calcd for (C24H30YCl)2
(mol wt 885.72): C, 65.09; H, 6.83. Found: C, 65.19; H, 6.60.
B is [((c y c lo h e x y lid e n e m e t h y l)c y c lo p e n t a d ie n y l)-
m eth ylyttr iu m ] (7a ). To a solution of 7 (0.166 g, 0.187 mmol)
in toluene (15 mL) was added MeLi (0.12 mL, 1.5 M in Et2O)
at -78 °C, and the reaction mixture was stirred for 6 h. The
solvent was removed under vacuum (10-2 mbar), leaving a
colorless solid which could not be purified by crystallization.
2
1H NMR (benzene-d6, 200 MHz): δ -0.61 (t, 6H, J (89Y,1H) )
3.1 Hz) and signals of the educt. MS (205 °C; m/z (%)): 709
(0.4) [(C12H14)3Y2Me2]+, 421 (0.3) [(C12H14)3Y2Me]+, 407 (110)
[C24H30Y]+, and educt signals.
Bis((cycloh e xylid e n e m e t h yl)cyclop e n t a d ie n yl)b is-
(tetr a h yd r ofu r a n )sa m a r iu m (8). To a suspension of SmI2-
(THF)2 (1.23 g, 2.24 mmol) in THF (50 mL) was added
K[C5H4CHdC6H10] (6; 0.88 g, 4.48 mmol) at room temperature.
After the reaction mixture was stirred for 12 h, it was filtered.
Then the solvent was removed from the filtrate under vacuum
(10-2 mbar). The remaining black oil was washed with pentane
(20 mL) and dried, yielding 0.59 g (43%) of a black powder of
During the purification process of 11, a few colorless crystals
of the hydrolyzation product [(Me2CdCHC5H4)2Y(Et2O)]2(µ-O)
(12) were isolated and characterized by X-ray diffraction
analysis.
T r is ((2-m e t h y l-1-p r o p e n y l)c y c lo p e n t a d ie n y l)(t e t -
r a h yd r ofu r a n )sa m a r iu m (13). In analogy to the preparation
of 11, SmCl3 (0.75 g, 3 mmol) suspended in THF (80 mL) was
reacted with K[C5H4CHdCMe2] (10: 1.40 g, 9 mmol) to provide
1.05 g (61%) of red crystals of 13; mp 91 °C dec. 1H NMR
(benzene-d6, 400 MHz): δ 13.72 (sbr, 6 H, CH, Cp), 13.57 (sbr,
6 H, CH, Cp), 3.35 (s, 3 H, CH), 1.14 (s, 9 H, CH3), 0.46 (s, 9
H, CH3), -2.46 (sbr, 4 H, THF), -4.12 (sbr, 4 H, THF). 13C{1H}
NMR (benzene-d6, 100.64 MHz): δ 130.91 (-Cd), 122.16 (CH),
115.62 (C-C4H7), 104.80 (CH, Cp), 104.63 (CH, Cp), 64.30 (br,
CH2, THF), 27.50 (CH3), 19.93 (CH3), 18.61 (CH2, THF). MS
1
8; mp 98 °C. H NMR (pyridine-d5, 200 MHz): δ 13.33 (sbr, 4
H, CH, Cp), 12.56 (sbr, 4 H, CH, Cp), 3.66 (m, 8 H, THF), 2.35
(sbr, 2 H, CH), 1.63 (m, 8 H, THF), (m, 20 H, CH2). 13C{1H}
NMR (pyridine-d5, 50.32 MHz): δ 131.44 (CH), 127.68 (-Cd
), 115.62 (Cqu, Cp), 105.50 (CH, Cp), 103.57 (CH, Cp), 67.43
(CH2, THF), 38.44 (CH2), 30.23 (CH2), 26.91 (CH2), 26.39 (CH2),
26.34 (CH2), 25.41 (CH2, THF). MS (152Sm, 204 °C; m/z (%)):
472 (100) [M + 2H, - 2THF]+, 470 (99) [M - 2THF]+, 311
(26) [C12H15Sm]+, 160 (42) [C12H16]+, 145 (9), 131 (20), 117 (24),
104 (5). Anal. Calcd for C32H46SmO2 (mol wt 613.02): C, 62.69;
H, 7.56. Found: C, 61.92; H, 6.72.
(
152Sm, 132 °C; m/z (%)): 509 (14) [M - THF]+, 390 (100)
[C18H22Sm]+, 271 (42) [C12H15Sm]+, 119 (15) [C9H11]+, 105 (13).
Anal. Calcd for C31H41SmO (mol wt 580.03): C, 64.19; H, 7.12.
Found: C, 64.28; H, 6.71.
T r is ((c y c lo h e x y lid e n e m e t h y l)c y c lo p e n t a d ie n y l)-
(tetr a h yd r ofu r a n )sa m a r iu m (9). To a suspension of SmCl3
(0.58 g, 2.26 mmol) in THF (80 mL) was added K[C5H4CHd
C6H10] (6; 1.35 g, 6.8 mmol) was added at room temperature,
and the reaction mixture was stirred for 12 h. After removal
of the solvent under vacuum (10-2 mbar), the residue was
washed with pentane (20 mL) and extracted with toluene (50
mL). The toluene extract was concentrated and cooled to -25
°C, yielding 1.13 g (71%) of red crystals of 9; mp 109 °C. 1H
NMR (benzene-d6, 200 MHz): δ 13.96 (sbr, 6 H, CH, Cp), 13.50
(sbr, 6 H, CH, Cp), 2.77 (s, 3 H, CH), 2.35-2.25 (m, 6 H, CH2),
1.60-0.87 (m, 24 H, CH2), -2.50 (sbr, 4 H, THF), -4.20 (sbr, 4
H, THF). 13C{1H} NMR (benzene-d6, 50.32 MHz): δ 132.05
(CH), 128.29 (-Cd), 115.37 (C-C7H11), 105.95 (CH, Cp),
105.06 (CH, Cp), 67.36 (CH2, THF), 38.90 (CH2), 30.61 (CH2),
27.42 (CH2), 26.86 (CH2), 26.83 (CH2), 19.30 (CH2, THF). MS
(1 ,1 -B i s (m e t h y l e n e c y c l o p e n t a d i e n y l )e t h e n e )-
d ip ota ssiu m (14). To a solution of Na[C5H5] (21.13 g, 240
mmol) in THF (180 mL) was added 3-chloro-2-(chloromethyl)-
1-propene (9.26 mL, 80 mmol) at -20 °C. After it was stirred
for 24 h at -20 °C, the reaction mixture was filtered and the
solvent was removed from the filtrate under vacuum (10-2
mbar). The remaining oily residue was stirred for 2 h under
vacuum and was then extracted with hexane (120 mL).
Removal of hexane from the extract left a yellow liquid (11.36
g, 61.5 mmol), which was immediately dissolved in THF (150
mL). Then potassium hydride (4.94 g, 123 mmol) was added
to this solution at -20 °C. The brown reaction mixture was
stirred for 24 h at this temperature and was then filtered at
room temperature and the filtrate concentrated to 30 mL. After
addition of hexane (50 mL) the mixture was again stirred for
1 h. The yellow sticky residue remaining after removal of the
solvents by decantation was washed twice with a mixture (1:1
v/v) of hexane and diethyl ether (50 mL), yielding 13.74 g (66%)
(
152Sm, 84 °C; m/z (%)): 629 (8) [M - THF]+, 470 (100) [C24H30
-
Sm]+, 311 (29) [C12H15Sm]+, 160 (84) [C12H16]+, 145 (16), 131
(33), 117 (40), 104 (20). Anal. Calcd for C40H53SmO (mol wt
700.22): C, 68.61; H, 7.63. Found: C, 68.37; H, 7.48.
1
of 14 as a yellow pyrophoric powder; mp 223 °C dec. H NMR
(2-Meth yl-1-p r op en ylcyclop en ta d ien yl)p ota ssiu m (10).
In analogy to the preparation of 6, 5-(2-methyl-1-propenyl)-
cyclopentadiene (4.74 g, 39 mmol) was reacted with K[N-
(SiMe3)2] (7.78 g, 39 mmol) in THF (150 mL) to provide 6.01 g
(97%) of a pyrophoric beige powder of 10; mp 146 °C. 1H NMR
(pyridine-d5, 200 MHz): δ 6.11-6.08 (m, 4 H, CH), 5.98-5.93
(m, 4 H, CH), 5.23 (s, 2 H, dCH2), 3.86 (s, 4 H, CH2). 13C{1H}
NMR (pyridine-d5, 50.32 MHz): δ 155.25 (-Cd), 119.01 (d
CH2), 109.0 (C-Cp), 104.89 (CH, Cp), 103.69 (CH, Cp), 40.02
(CH2). MS (147 °C; m/z (%)): 184 (82) [C14H16]+, 169 (82)

122 Organometallics, Vol. 22, No. 1, 2003
Ta ble 1. Cr ysta l Str u ctu r e Deter m in a tion of 3, 5b, a n d 7
Schumann et al.
3
5b
7
formula
fw
C
651.6
26H38KOLuCl2
C46H76B2LiO2SmCl2
910.9
0.30 × 0.05 × 0.20; yellow
monoclinic
C2/c
C48H60Y2Cl2‚C7H8
488.9
cryst size (mm3); color
cryst syst
space group
Z (formula units)
a (Å)
0.40 × 0.24 × 0.08; yellow
monoclinic
Cc
0.40 × 0.26 × 0.22; colorless
triclinic
P1h
1
4
4
11.3332(2)
27.3575(3)
8.8820(2)
90
103.5380(10)
90
2677.33(8)
1.611
1296
29.5008(3)
12.8306(2)
13.53190(10)
90
115.6220(10)
90
4618.33(9)
1.310
1908
6.5351(2)
12.4006(4)
15.4309(6)
104.2920(10)
95.3160(10)
96.8640(10)
1193.38(7)
1.361
510
2.567
3-55
9011
b (Å)
c (Å)
R (deg)
â (deg)
γ (deg)
V (Å3)
dcalcd (g cm-3
F(000)
)
µ (mm-1
)
4.058
3-52
7615
1.422
3-55
17 220
2θ range (deg)
no. of rflns collected
no. of unique rflns
4911
5303
5392
abs cor, max/min
1.0000/0.4382
3686
4911/63/276
0.0567/0.0740
0.1214/0.1262
0.932
0.8253/0.5959
4557
5301/0/249
0.0404/0.0561
0.0717/0.0765
1.089
0.6647/0.5006
3453
5392/0/264
0.0560/0.1117
0.0950/0.1128
0.969
no. of obsd rflns, I >2σ(I)
no. of data/restraints/params
R1 (I > 2σ(I), all data)a
wR2 (I > 2σ(I), all data)b
goodness of fitc
weighting const a/bd
0.0105/0
2.348/-3.156
0.0214/1.2687
0.963/-1.274
0.0168/0
0.885/-1.067
diff peak/hole (e Å-3
)
R1 ) ∑(||Fo| - |Fc||)/∑|Fo|. wR2 ) [∑w(|Fo| - |Fc|)2/∑w|Fo| ]1/2
.
c GOF ) [∑w(|Fo| - |Fc|)2/(n - p)]1/2
.
w ) 1/[σ2(Fo2) + (aP)2 + bP], P
a
b
2
d
) (Fo + 2Fc2)/3.
2
Ta ble 2. Cr ysta l Str u ctu r e Deter m in a tion of 2a
a n d 12
[C13H13]+, 155 (31), 143 (27), 135 (14), 128 (44), 117 (36), 104
(40), 91 (55), 77 (58), 66 (16), 51 (20), 41 (26), 39 (27). Anal.
Calcd for C14H14K2: (mol wt 260.46): C, 64.56; H, 5.42.
Found: C, 64.36; H, 5.90.
2a
12
formula
C
609.5
30H50LiO2YCl2
C44H64O3Y2
818.8
a n sa -[1,1-Bis(m e t h yle n e cyclop e n t a d ie n yl)e t h e n e ]-
(tetr a h yd r ofu r a n )lu tetiu m Ch lor id e (15). To a suspension
of LuCl3(THF)3 (1.15 g, 2.31 mmol) in THF (50 mL) was added
K2[H2CdC(CH2C5H4)2] (14; 0.6 g, 2.31 mmol) at room temper-
ature. The reaction mixture was stirred for 6 h and was then
filtered. After removal of the solvent from the filtrate under
vacuum (10-2 mbar), the residue was extracted with diethyl
ether (50 mL). The resulting ether solution was evaporated,
yielding 0.15 g (14%) of a white powder of 15; mp 192 °C dec.
1H NMR (pyridine-d5, 200 MHz): δ 6.14 (s, 4 H, CH), 6.10 (s,
4 H, CH), 5.06 (s, 2 H, dCH2), 3.64 (m, 4 H, THF), 3.38 (s, 4
H, CH2), 1.59 (m, 4 H, THF). 13C{1H} NMR (pyridine-d5, 50.32
MHz): δ 147.89 (CdCH2), 113.41 (CH), 112.57 (dCH2), 109.85
(CH), 67.38 (CH2, THF), 36.66 (CH2), 25.33 (CH2, THF). MS
fw
cryst size (mm3); color
0.40 × 0.32 × 0.25; 0.80 × 0.50 × 0.40;
pale yellow
monoclinic
P21/c
pale yellow
monoclinic
P21/n
cryst syst
space group
Z (formula units)
a (Å)
b (Å)
c (Å)
4
2
15.953(7)
14.702(6)
13.952(6)
92.66(3)
3269(2)
1.238
1288
1.970
4-55
7764
11.3097(3)
15.4902(4)
11.8711(2)
100.257(1)
2046.46(8)
1.329
860
2.858
4-61
15 217
â (deg)
V (Å3)
dcalcd (g cm-3
F(000)
)
µ (mm-1
)
2θ range (deg)
no. of rflns collected
no. of unique rflns
abs cor, max/min
(
175Lu, 238 °C; m/z (%)): 392 (47) [M - THF]+, 356 (100)
7455
none
4707
0.4490/0.2568
3562
[C14H14Lu]+, 313 (12), 302 (18) [C10H8Lu]+, 291 (8) [C9H10Lu]+,
277 (25) [C8H8Lu]+, 238 (13) [C5H5Lu]+, 184 (89) [C14H16]+, 169
(70), 155 (36), 141 (40), 129 (46), 117 (59), 104 (75), 91 (53), 77
(70). Anal. Calcd for C18H22LuClO (mol wt 464.79): C, 46.51;
H, 4.77. Found: C, 46.71; H, 5.48.
no. of obsd rflns, I >2σ(I) 3742
no. of data/restraints/
params
7455/1/337
4707/0/229
R1 (I > 2σ(I), all data)a
0.0703/0.1763
0.0350/0.0736
0.0585/0.0827
1.037
0.0339/0.7952
0.887/-0.427
wR2 (I > 2σ(I), all data)b 0.1763/0.2217
X-r a y St r u ct u r e Det er m in a t ion . The crystal data and
details of data collection of 2a , 3, 5b, 7, and 12 are given in
Tables 1 and 2. Data sets were collected at 173 K on a Siemens
SMART CCD diffractometer16 (ω scans, λ ) 0.710 73 Å,
graphite-monochromated Mo KR radiation). The structures
were solved by direct methods using SHELXS-9717 and were
refined on F2 using all observed reflections with SHELXL-97.18
All non-hydrogen atoms were refined anisotropically. The
hydrogen atoms were placed in calculated positions (C-H )
0.96 Å) and assigned to an isotropic displacement parameter
goodness of fitc
1.023
0.1139/0
1.296/-0.818
weighting const a/bd
diff peak/hole (e Å-3
)
a
b
2
R1 ) ∑(||Fo| - |Fc||)/∑|Fo|. wR2 ) [∑w(|Fo| - |Fc|)2/∑w|Fo| ]1/2
.
c GOF ) [∑w(|Fo| - |Fc|)2/(n - p)]1/2
.
w ) 1/[σ2(Fo2) + (aP)2
+
d
bP], P ) (Fo + 2Fc2)/3.
2
of 0.08 Å2). SADABS19 was used to perform area detector
scaling and absorption corrections for the data of 3, 5b, 7, and
12. In 3, one cyclopentadienyl ligand as well as the vinyl group
attached to the second cyclopentadienyl ligand were disordered
and were therefore refined with isotropic displacement pa-
rameters. Further material is part of the Supporting Informa-
(16) SMART and SAINT. DataCollection and Processing Software
for SMART System; Siemens Analytical X-ray Instruments, Inc.,
Madison, WI, 1995.
(17) Sheldrick, G. M. SHELXS-97, Program for Crystral Structure
Determination; Universita¨t Go¨ttingen, Go¨ttingen, Germany, 1997.
(18) Sheldrick, G. M. SHELXL-97, Program for Crystral Structure
Determination; Universita¨t Go¨ttingen, Go¨ttingen, Germany, 1997.
(19) Sheldrick, G. M. SADABS, Program for Empirical Absorption
Correction of Area Detector Data; Universita¨t Go¨ttingen, Go¨ttingen,
Germany, 1996.

Organometallic Compounds of the Lanthanides
Organometallics, Vol. 22, No. 1, 2003 123
Sch em e 1
F igu r e 1. ORTEP plot23 of the molecular structure and
the numbering scheme of 2a with 30% probability thermal
ellipsoids. The hydrogen atoms are not depicted. Selected
bond lengths (Å) and bond angles (deg) with estimated
standard deviations in parentheses (Cp(1) and Cp(2) define
the centroid positions of the ring atoms C(1-5), and C(21-
25), respectively): Y-Cp(1) ) 2.386(3), Y-Cp(2) ) 2.386-
(3), Y-Cl(1) ) 2.628(2), Y-Cl(2) ) 2.621(2), Cl(1)-Li )
2.396(11), Cl(2)-Li ) 2.420(11), Li-O(1) ) 1.946(11), Li-
O(2) ) 1.935(12); Cp(1)-Y-Cp(2) ) 137.03(11), Cl(1)-Y-
Cp(1) ) 106.98(9), Cl(1)-Y-Cp(2) ) 104.84(9), Cl(2)-Y-
Cp(2) ) 106.53(9), Cl(2)-Y-Cp(1) ) 104.37(9), Cl(1)-Y-
Cl(2) ) 84.91(7), Li-Cl(1)-Y ) 90.3(3), Li-Cl(2)-Y )
90.0(3).
tion. The geometrical aspects of the structures were analyzed
by using PLATON software.20
Resu lts a n d Discu ssion
B is (t e t r a m e t h y lv in y lc y c lo p e n t a d ie n y l)la n -
th a n id e Ch lor id es. The trichlorides of yttrium, sa-
marium, and lutetium react in THF at room tempera-
ture with 2 equiv of (tetramethylvinylcyclopentadienyl)-
lithium (1a), which in turn is prepared from butyllithium
and the isomeric mixture of tetramethylvinylcyclopen-
tadiene and 5-ethylidene-1,2,3,4-tetramethyl-1,3-cyclo-
pentadiene,12 to give the crystalline lithium chloride
adducts (CH2dCHC5Me4)2Ln(µ-Cl)2Li(OEt2)2 (Ln ) Y
(2a ), Sm (2b), Lu (2c)) in 45-60% yield (Scheme 1).
The pale yellow (2a ,c) or orange complexes (2b) melt
with decomposition and are slightly pyrophoric. De-
pending on the duration of the drying process of the
crystals under vacuum, the analytical data of the
complexes indicate some loss of diethyl ether, as already
stated earlier for other compounds of this type.21 The
new complexes 2a -c are soluble in polar solvents and
in aromatic hydrocarbons. In contrast to the noncrystal-
line products which we isolated from the reactions of
LnCl3 with Li[C5Me4CH2CH2CHdCH2],4 the complexes
2 readily crystallize from diethyl ether below 0 °C.
Obviously, the dangling butenyl substituents prevent
crystallization. The yttrium complex 2a crystallizes in
the monoclinic space group P21/c. The molecular struc-
ture (Figure 1) shows for both metals, the yttrium and
the lithium atom, the typical distorted-tetrahedral
ligand arrangement. The dicyclopentadienyllanthanide
unit and the lithium dietherate moiety are bridged by
two chlorine atoms. The bond lengths Cpc-Y (2.39 Å),
Cl-Y (2.62 Å), and Li-Cl (2.41 Å) are in accordance
with the respective values in (C5Me5)2Y(µ-Cl)2Li(THF)2.22
In contrast to the above-described reactions, no mon-
omeric complex is formed when LuCl3(THF)3 is reacted
in THF with 2 equiv of (tetramethylvinylcyclopentadi-
enyl)potassium (1b), the latter being prepared from
K[N(SiMe3)2] and the isomeric mixture of tetrameth-
Sch em e 2
ylvinylcyclopentadiene and 5-ethylidene-1,2,3,4-tetra-
methyl-1,3-cyclopentadiene (Scheme 2). The reaction
affords a pale yellow powder which is soluble in boiling
toluene but almost insoluble in ether and other donor
solvents such as THF and pyridine. Whereas cooling of
the toluene solution did not afford a crystalline product,
pale yellow crystals separated from the ethereal solution
obtained by extraction of the solid immediately after
isolation from the reaction mixture. The crystals proved
to be suitable for X-ray diffraction analysis. The result
of the structure determination shows the monosolvated
complex [(CH2dCHC5Me4)2Lu(µ-Cl)2K(THF)]n (3) (Fig-
ure 2a), forming polymeric chains (Figure 2b).
As in the solid-state structure of the yttrium complex
2a , the coordination geometry around the lutetium atom
is that of a distorted tetrahedron formed by the ring
centroids of the two cyclopentadienyl ligands and by two
bridging chlorine atoms, whereas the coordination
(20) Spek, A. L. PLATON. Acta Crystallogr. 1990, 4, C34.
(21) Schumann, H.; Albrecht, I.; Loebel, J .; Hahn, E.; Bilayet
Hossain, M.; van der Helm, D. Organometallics 1986, 5, 1296.
(22) Evans, W. J .; Boyle, T. J .; Ziller, J . W. Inorg. Chem. 1992, 31,
1120.

124 Organometallics, Vol. 22, No. 1, 2003
Schumann et al.
99.8°, respectively, correspond very well with the re-
spective values of the cerium complex (136, 86.5, and
98.3°). The Cpc-Lu-Cl angles, ranging from 105.9 to
106.5°, are almost identical with those of the cerium
compound (105.4-106.2°). Due to the difference in the
ionic radii of Lu(III) and Ce(III), the bond distances Lu-
C(Cp) (2.58-2.68 Å) and Lu-Cl (2.57 and 2.58 Å) are
shorter than the Ce-C(Cp) (2.77-2.83 Å) and the Ce-
Cl distances (2.77 and 2.78 Å). The trigonal-bipyramidal
coordination geometry around the potassium atom is
formed by the Cl(2) and Cl(2)′ atoms in the axial
positions and by Cl(1), Cl(1)′′, and the oxygen of the THF
ligand occupying the corners of the equatorial plane. The
Cl(1)-K-Cl(1)′′, Cl(1)-K-O, and Cl(1)′′-K-O angles
of 124, 116, and 113.4° estimated for 3 are closer to the
ideal value of 120° than the comparable values of the
cerium complex (128.7, 104.3, and 124.6°). However, the
Cl(2)-K-Cl(2)′ angles of 146.8° for 3 and 156.1° for the
cerium complex are far from the 180° angle demanded
for a regular trigonal bipyramid.
The very broadened signals in the NMR spectra of 3
indicate the existence of oligomeric structures even in
solution. All attempts to remove the potassium chloride
from 3 in order to get the complex [(CH2dCHC5Me4)2-
LuCl]n were unsuccessful. Sublimation of 3 or its
treatment with polar solvents caused decomposition or
formation of insoluble products, respectively.
B is (t e t r a m e t h y lv in y lc y c lo p e n t a d ie n y l)la n -
th a n id e Alk yls. Alkyl lanthanide complexes play a key
role as precatalysts in organolanthanide-mediated reac-
tions.2 Our recent results concerning the alkylation of
ω-alkenyl-functionalized cyclopentadienyllanthanide chlo-
rides indicate that it is very difficult to generate stable
σ-Ln-C bonds in the presence of alkenyl substituents
at the cyclopentadienyl ligands.4 The expected alkyl
complexes are unstable in solution and decompose via
insertion reactions.4 Despite these discouraging experi-
ences, but aware of the better crystallization properties
of (vinylcyclopentadienyl)lanthanide complexes, we in-
vestigated the metathetical reactions of the complexes
2a -c with methyllithium and (bis(trimethylsilyl)meth-
yl)lithium in order to get the corresponding alkyl
derivatives (CH2dCHC5Me4)2LnR (R ) Me, CH(SiMe3)2).
The reactions were conducted in diethyl ether at -78
°C. The products formed are extremely sensitive and
decompose even under an inert atmosphere at this low
temperature within a few minutes. The exchange of
diethyl ether for nonpolar solvents such as cyclohexane,
benzene, and toluene, or carrying out the reactions in
deuterated solvents in order to get interpretable NMR
spectra immediately after the end of the reactions, does
not lead to satisfying results. Increasing amounts of
insoluble polymeric solids precipitate during these
manipulations, thus indicating that the products them-
selves are already catalytically active and self-polymer-
izing. Comparable to the results of Watson25 and
F igu r e 2. (a, top) ORTEP plot23 of the molecular structure
and the numbering scheme of 3 with 30% probability
thermal ellipsoids. The hydrogen atoms and the disorder
are not depicted. Selected bond lengths (Å) and bond angles
(deg) with estimated standard deviations in parentheses
(Cp(1A), Cp(1B), and Cp(2) define the centroid positions
of the ring atoms C(1A-5A), C(1B-5B), and C(21-25),
respectively): Lu-Cp(1A) ) 2.318(8), Lu-Cp(1B) ) 2.332-
(12), Lu-Cp(2) ) 2.343(7), Lu-Cl(1) ) 2.571(3), Lu-Cl(2)
) 2.579(3), K-O ) 2.665(12), K-Cl(1) ) 3.116(5), K-Cl-
(1)′′ ) 3.123(5), K-Cl(2)′ ) 3.157(5), K-Cl(2) ) 3.163(4),
K-K′ ) 4.635(2); Cp(1A)-Lu-Cp(2) ) 134.8(2), Cp(1B)-
Lu-Cp(2) ) 134.6(3), Cp(1A)-Lu-Cl(1) ) 106.3(2), Cp-
(1A)-Lu-Cl(2) ) 105.97(14), Cp(1B)-Lu-Cl(1) ) 106.5(2),
Cp(1B)-Lu-Cl(2) ) 106.0(2), Cp(2)-Lu-Cl(1) ) 105.9(2),
Cp(2)-Lu-Cl(2) ) 105.9(2), Cl(1)-Lu-Cl(2) ) 88.48(11),
Cl(1)-K-Cl(2) ) 69.82(10), Cl(1)-K-Cl(1)′′ ) 124.0(2), Cl-
(1)-K-Cl(2)′ ) 80.37(11), Cl(1)′′-K-Cl(2)′ ) 130.36(13),
Cl(1)′′-K-Cl(2) ) 80.18(11), Cl(2)′-K-Cl(2) ) 146.81(14),
O-K-Cl(1) ) 116.0(3), Cl(1)′′-K-O = 113.4(3), O-K-Cl-
(2) ) 96.4(3), O-K-Lu ) 115.2(3), Lu-Cl(1)-K ) 100.51-
(12), Lu-Cl(2)-K ) 99.12(12), Lu-Cl(1)-K′ ) 148.08(14),
Lu-Cl(2)-K′′ ) 141.84(14), K-Cl(1)-K′ ) 95.97(11), K′′-
Cl(2)-K ) 94.35(9). Applied symmetry operations: (′) x,
-y, z + 0.5; (′′) x, -y, z - 0.5. (b, bottom) Unit cell plot23 of
[(CH2dCHC5Me4)2Lu(µ3-Cl)2K(THF)]n (3), showing three
chains along the c axis.
geometry of the respective alkali metal changes from a
distorted tetrahedron in 2a to a highly distorted trigonal
bipyramid in 3. Each potassium atom is coordinated by
one THF molecule and four chlorine atoms which belong
to three different monomeric units. Each chlorine atom
is µ3-coordinated to one lutetium and two potassium
atoms. The only complex in the literature which shows
the same remarkable structure is the cerium compound
[(C5Me5)2Ce(µ3-Cl)2K(THF)n.24 The angles Cpc-Lu-Cpc,
Cl(1)-Lu-Cl(2), and Lu-Cl(1/2)-K of 135, 88.5, and
(23) Bergerhoff, G.; Brandenburg, K.; Berndt, M., DIAMOND,
Visuelles Informationssystem fu¨r Kristallstrukturen; Universita¨t Bonn,
Bonn, Germany, 1996.
(24) Evans, W. J .; Olofson, J . M.; Zhang, H.; Atwood, J . L. Organo-
metallics 1988, 7, 629.
(25) (a) Watson, P. L. J . Chem. Soc., Chem. Commun. 1983, 276.
(b) Watson, P. L. J . Am. Chem. Soc. 1983, 105, 6491. (c) Watson, P. L.
In Selective Hydrocarbon Activation; Davies, J . A., Watson, P. L.,
Liebman, J . F., Greenberg, A., Eds.; VCH: New York, 1990.

Organometallic Compounds of the Lanthanides
Organometallics, Vol. 22, No. 1, 2003 125
Sch em e 3
Sch em e 4
Bercaw26 concerning several lanthanidocene alkyl com-
plexes, the spatial vicinity of the double bonds to the
metal center will probably cause CH activation followed
by insertion of the alkene moiety into the σ-Ln-C bond.
The only compound from which we could isolate a few
crystals is the yttrium methyl derivative (CH2dCHC5-
Me4)2Y(µ-CH3)2Li(THF)2 (4), stabilized by 1 equiv of
methyllithium (Scheme 3). This “ate” complex could be
definitely characterized only by NMR spectroscopy,
since its extremely low thermal stability prevents the
application of all other analytical methods, including
X-ray diffraction. The crystals decompose slowly even
at -78 °C.
Whereas the reactions of 2a -c with KN[(SiMe3)2],
which are expected to generate the amide complexes
(CH2dCHC5Me4)2LnN(SiMe3)2, take the same complex
course as the alkylation reactions, the isolation of
(CH2dCHCH2CH2C5Me4)2SmN(SiMe3)2 was successful.4
We assume that the vinyl group is more reactive than
the 3-butenyl moiety and inserts even into a Ln-N
bond.
B is {(2-(9-b o r a b ic y c lo [3.3.1]n o n -9-y l)e t h y l)-
t et r a m et h ylcyclop en t a d ien yl}la n t h a n id e Ch lo-
r id es. The vinyl substituents of the cyclopentadienyl
ligands of the bis(tetramethylvinylcyclopentadienyl)-
lanthanide chlorides 2a -c should be suitable for the
introduction of borane groups via hydroboration. Since
our previous experiences showed that a further func-
tionalization of the alkenyl side chains of lanthani-
docenes and, especially, the isolation of the respective
products is rather difficult, the highly selective 9-bora-
bicyclo[3.3.1]nonane (9-BBN) was chosen as hydrobo-
ration agent.
The three complexes 2a -c react with 2 equiv of
9-BBN in toluene at room temperature, producing the
crystalline compounds (C8H14BCH2CH2C5Me4)2Ln(µ-
Cl)2Li(THF)2 (Ln ) Y (5a ), Sm (5b), Lu (5c)) in yields
of 70-90% (Scheme 4). No isomeric products are formed.
The borane selectively attacks the terminal vinylic
carbon atom.
marium atom (two cyclopentadienyl groups and two
chlorine atoms) and the lithium atom (two chlorine
atoms and two THF molecules), which is typical of
alkali-metal halide adducts of lanthanide complexes of
this type. When the difference in the ionic radii of Sm-
(III) and Y(III) is taken into account, the bond distances
and bond angles in 5b are in accordance with those
estimated for (CH2dCHC5Me4)2Y(µ-Cl)2Li(OEt2)2 (2a ).
The attempts to synthesize the ansa-lanthanidocene
complexes RB(CH2CH2C5Me4)2LnCl were not successful.
The reactions of 2a -c with BH3(THF), ClBH2(SMe2),
or Me2CHCMe2BH2 did not allow the isolation of any
identificable hydroboration products. The obviously
nonregioselective course of the reactions led to product
mixtures which could not be separated into their
components either by crystallization or by sublimation.
In view of the fact that in 5a -c the alkenyl functions
of the starting lanthanidocene chlorides 2a -c are
saturated by addition of the 9-BBN borane, the alky-
lation of these hydroborated complexes should be more
promising, since C-H activation followed by insertion
reactions can no longer disturb the course of the
alkylation reactions. However, although the NMR spec-
tra of the crude products obtained from the reactions of
5a -c with LiCH(SiMe3)2 as the alkylating agent give
some indication of the formation of complexes such as
(C8H14BCH2CH2C5Me4)2LnCH(SiMe3)2, no pure and
crystalline products could be isolated.
(Cycloh exylid en em eth yl)cyclop en ta d ien yl a n d
(2-Meth yl-1-pr open yl)cyclopen ta dien yl Com plexes
of Yttr iu m a n d Sa m a r iu m . Since the synthesis of
borane-bridged ansa-lanthanidocenes via hydroboration
of the unsubstituted vinyl functions of the complexes
2a -c did not achieve satisfying results, we postulated
that the use of lanthanidocenes containing already
substituted vinyl groups could still make this plan
succeed. To that purpose, first the potassium salts of
(2,4-cyclopentadien-1-ylidenemethyl)cyclohexane (6) and
5-isobutylidenecyclopentadiene (10) were prepared by
deprotonation of the corresponding fulvene derivatives13
with K[N(SiMe3)2], which then were reacted with YCl3
in THF at room temperature, giving the dimeric com-
plexes [(C6H10dCHC5H4)2Y(µ-Cl)]2 (7) and [(Me2Cd
CHC5H4)2Y(µ-Cl)]2 (11) in yields of 48 and 42%, respec-
The colorless (5a ) or yellow crystals (5b,c) are not
pyrophoric like their vinyl precursors 2a -c and melt
without decomposition at 128, 139, and 141 °C, respec-
tively. They are soluble in polar (diethyl ether, THF)
and aromatic solvents (toluene) and crystallize from
hexane or toluene at 0 °C. According to the results of
the elemental analyses of 5a ,c, both complexes lose the
two lithium-coordinated THF molecules under vacuum.
The molecular structure of (C8H14BCH2CH2C5Me4)2-
Sm(µ-Cl)2Li(THF)2 (5b) (Figure 3) shows a distorted-
tetrahedral ligand arrangement around both the sa-
(26) St. Clair, M.; Santersiero, B. D.; Bercaw, J . E. Organometallics
1989, 8, 17.

126 Organometallics, Vol. 22, No. 1, 2003
Schumann et al.
Sch em e 5
Sch em e 6
F igu r e 3. ORTEP plot23 of the molecular structure and
the numbering scheme of 5b with 30% probability thermal
ellipsoids. The hydrogen atoms are not depicted. Selected
bond lengths (Å) and bond angles (deg) with estimated
standard deviations in parentheses (Cp defines the centroid
position of the ring atoms C(1-5)): Sm-Cp ) 2.467(2),
Sm-Cl ) 2.7094(8), Cl-Li ) 2.370(6), Li-O ) 1.931(6),
B-C(11) ) 1.582(5), B-C(15) ) 1.587(5), B-C(19) ) 1.572-
(5); Cp-Sm-Cp′ ) 136.77(5), Cp-Sm-Cl ) 105.98(4), Cp-
Sm-Cl′ ) 105.47(4), Cl-Sm-Cl′ ) 85.25(4), Li-Cl-Sm
) 86.6(2), O′-Li-O ) 106.0(5), O-Li-Cl′ ) 116.39(10),
O-Li-Cl ) 108.47(9), Cl′-Li-Cl ) 101.5(3), C(11)-B-
C(15) ) 125.0(3), C(19)-B-C(11) ) 122.5(3), C(19)-B-
C(15) ) 111.8(3). Applied symmetry operations: (′) -x +
1, y, -z + 0.5.
steric reasons, the two cyclohexylidenemethyl substit-
uents of each Cp2YCl unit are trans-positioned.
In the course of our attempts to crystallize complex
11 from different solvents, we isolated a few crystals,
which, however, turned out to be the hydrolyzation
product of 11, [(Me2CdCHC5H4)2Y(OEt2)]2(µ-O) (12)
(Figure 5), probably formed by slight traces of water
being present when changing solvents. This fact dem-
onstrates impressively the extremely high oxophilicity
of such lanthanidocenes.
The most interesting parameters of the molecular
structure of 12 are the Y-O(1)-Y angle of 180° and the
short Y-O(1) distance of 2.05 Å, which, however,
correspond very well with the respective data for
[(C5H5)2Lu(THF)]2(µ-O) (180°/2.00 Å).29
tively (Schemes 5 and 6).While 7 is soluble in polar and
nonpolar solvents and can be crystallized from toluene
at -25 °C, the low solubility of 11 in nonpolar solvents
such as hexane and toluene prevents its crystallization.
The single-crystal X-ray structural analysis of 7
(Figure 4) shows a distorted-tetrahedral ligand arrange-
ment around each yttrium atom, as usually found for
these types of dimeric bis(cyclopentadienyl)lanthanide
halides.27 The bond distances and bond angles of 7 (Y-
Cl ) 2.68 Å, Y-Cpc ) 2.34 Å; Cpc-Y-Cpc ) 129°, Cl-
Y-Cl′ ) 82°) correspond well with the values of [(Me3-
SiC5H4)2Y(µ-Cl)]2 (2.69, 2.34 Å; 130, 81.6°).28 Due to
The sterically demanding C6H10dCH moiety at the
cyclopentadienyl ligands of the yttrium compound 7
probably will prevent interactions of the double bond
(28) Evans, W. J .; Sollberger, M. S.; Shreeve, J . L.; Olofson, J . M.;
Hain, J . H.; Ziller, J . W. Inorg. Chem. 1992, 31, 2492.
(29) Schumann, H.; Palamidis, E.; Loebel, J . J . Organomet. Chem.
1990, 384, C49.
(27) Schumann, H.; Meese-Marktscheffel, J . A.; Esser, L. Chem. Rev.
1995, 95, 865.

Organometallic Compounds of the Lanthanides
Organometallics, Vol. 22, No. 1, 2003 127
Sch em e 7
F igu r e 4. ORTEP plot23 of the molecular structure and
the numbering scheme of 7 with 30% probability thermal
ellipsoids. The hydrogen atoms are not depicted. Selected
bond lengths (Å) and bond angles (deg) with estimated
standard deviations in parentheses (Cp(1) and Cp(2) define
the centroid positions of the ring atoms C(101-105), and
C(201-205), respectively): Y-Cp(1) ) 2.334(2), Y-Cp(2)
) 2.349(2), Y-Cl ) 2.6749(11), Y-Cl′ ) 2.6934(11); Cp-
(1)-Y-Cp(2) ) 128.92(7), Cp(1)-Y-Cl ) 107.48(6), Cp-
(1)-Y-Cl′ ) 107.05(6), Cp(2)-Y-Cl ) 107.28(6), Cp(2)-
Y-Cl′ ) 113.85(6), Cl-Y-Cl′ ) 82.03(4), Y-Cl-Y′ )
97.97(4). Applied symmetry operations: (′) -x +2, -y + 1,
-z + 2.
7). Thesignals expected for the protons of the cyclopen-
tadienyl ligands of 7a cannot be assigned because of
superposition with the respective signals of the educt
7. Further proof for the formation of the methyl complex
is the presence of the monomeric methyl fragment
[(C7H11C5H4)2YCH3] in the mass spectrum. In conclu-
sion it can be noted that, at least in this case, the
substitution of a â-vinyl proton by a space-demanding
group slows down the interactions between the double
bond and the metal center, although autocatalytic
decomposition reactions prevent the isolation of the
methyl complex 7a .
In the frame of our investigations concerning the
behavior of samarium halides toward the potassium
salts 6 and 10, we started with the reaction of SmI2 with
2 equiv of 6 (Scheme 7), keeping in mind that it was
not possible to isolate the analogous ω-butenyl-substi-
tuted bis(cyclopentadienyl)samarium(II) derivative.4 The
resulting black solid is soluble in toluene and THF but
rather insoluble in hexane and diethyl ether. Elemental
analysis and NMR and mass spectra prove its formula-
tion as the THF-stabilized Sm(II) derivative (C6H10d
CHC5H4)2Sm(THF)2 (8). The remarkable upfield shift
1
of the H NMR signal of the single proton at the double
F igu r e 5. ORTEP plot23 of the molecular structure and
the numbering scheme of 12 with 30% probability thermal
ellipsoids. The hydrogen atoms are not depicted. Selected
bond lengths (Å) and bond angles (deg) with estimated
standard deviations in parentheses (Cp(1) and Cp(2) define
the centroid positions of the ring atoms C(1-5), and C(21-
25), respectively): Y-Cp(1) ) 2.4267(11), Y-Cp(2) )
2.4325(12), Y-O(1) ) 2.0466(2), Y-O(2) ) 2.3918(18); Cp-
(1)-Y-Cp(2) ) 129.77(4), Y-O(1)-Y′ ) 180.0, Cp(1)-Y-
O(2) ) 102.11(5), Cp(2)-Y-O(2) ) 101.95(6), O(1)-Y-
Cp(1) ) 109.24(3), O(1)-Y-Cp(2) ) 110.66(3), O(1)-Y-
O(2) ) 97.09(5). Applied symmetry operations: (′) 1 - x, 1
- y, 1 - z.
bond from 6.51 ppm in the potassium salt 6 to 2.35 ppm
may indicate a participation of the double bond in the
coordination to the metal center. Unfortunately, all
attempts to get single crystals of 8 suitable for X-ray
analysis failed.
The reactions of SmCl3 with 2 equiv of the ligand salts
6 and 10 do not afford the respective bis(cyclopentadi-
enyl)samarium chlorides but their redistribution prod-
ucts, the tris(cyclopentadienyl)samarocenes (C6H10d
CHC5H4)3Sm(THF) (9) and (Me2CdCHC5H4)3Sm(THF)
(13) (Scheme 8). Such redistribution behavior is also
known for the complexes of the early lanthanides with
unsubstituted cyclopentadienyl ligands.30 On the other
hand, the (methylcyclopentadienyl)samarium complex
[(MeC5H4)2Sm(µ-Cl)(THF)]2 proved to be a stable com-
pound.31 The red complexes 9 and 13 are soluble in polar
and in aromatic solvents. Whereas 9 melts without
with the σ-Y-C bonds which should be formed by
alkylation of the complex. To answer this question, we
investigated the reaction of 7 with methyllithium in
toluene at -78 °C. After a reaction time of 6 h, the
solvent was removed under vacuum and replaced by
benzene-d6 to get a solution suitable for 1H NMR
spectroscopic measurements. The appearance of a signal
(30) Edelmann, F. T.; Poremba, P. In Synthetic Methods of Orga-
nometallic and Inorganic Chemistry; Herrmann, W. A., Brauer, G.,
Eds.; G. Thieme: Stuttgart, New York, 1997.
(31) Evans, W. J .; Keyer, R. A.; Ziller, J . W. J . Organomet. Chem.
1993, 450, 115.
1
at -0.61 ppm, split into a triplet by H89Y coupling (2J
) 3.1 Hz), clearly proves the existence of the methyl-
bridged dimer [(C6H10dCHC5H4)2Y(µ-CH3)]2 (7a) (Scheme

128 Organometallics, Vol. 22, No. 1, 2003
Schumann et al.
Sch em e 8
Sch em e 9
decomposition at 109 °C, 13 decomposes already at 91
°C. As in the H NMR spectrum of the above-described
Con clu sion
1
Sm(II) complex 8, the 1H NMR spectra of 9 and 13 show
an extreme upfield shift of the signal of the single proton
at the double bond from 6.51 ppm in the potassium salts
6 and 10 to 2.77 ppm for 9 and 3.35 ppm for 13. Again,
this fact may be interpreted as the participation of the
double bond in coordination to the samarium center.
Regardless of the kind of solvent, the complexes 9 and
13 are always obtained as amorphous powders, thus
preventing the estimation of their molecular structure.
a n sa -[1,1′-B is (m e t h y le n e c y c lo p e n t a d ie n y l)-
et h en e](t et r a h yd r ofu r a n )lu t et iu m Ch lor id e. The
hydroboration of the organolanthanide complexes 7, 9,
11, and 13 containing substituted vinyl groups turned
out to be not regioselective and hence generates insepa-
rable product mixtures. Therefore, we changed our
approach in looking for a vinylic ligand system suitable
to produce ansa-lanthanidocenes. Such vinylic ansa
complexes should probably allow the synthesis of well-
defined hydroboration products with the borane group
attached to the backbone of the bridging ligand system.
For these reasons, we synthesized the dipotassium salt
K2[(C5H4CH2)2CdCH2] (14) in two steps starting with
the reaction of 3-chloro-2-(chloromethyl)-1-propene
with cyclopentadienylsodium, followed by deprotona-
tion of the hydrocarbon formed with potassium hydride.
The dipotassium salt 14, a yellow pyrophoric powder,
reacts with equimolar amounts of LuCl3 in THF at
room temperature, producing the ansa complex [H2Cd
C(CH2C5H4)2]LuCl(THF) (15), but only in yields of 14%
(Scheme 9). The complex can be isolated from the crude
residue remaining after the removal of the solvent from
the reaction mixture, by extraction with diethyl ether.
The main part of the residue, consisting of polymers, is
insoluble. Unfortunately, the hydroboration of complex
15 does not afford clearly defined borane derivatives.
The first vinyl-functionalized bis(cyclopentadienyl)-
lanthanide chlorides were prepared from YCl3, SmI2,
SmCl3, and LuCl3 by their reaction with the alkali-metal
salts of the respective functionalized cyclopentadiene.
The complexes are stabilized either by formation of
alkali-metal halide adducts or by dimerization. The
substitution of the chloride by transmetalation with
lithium or potassium alkyls resulted in the formation
of extremely unstable lanthanidocene alkyl complexes.
After the formation of the σ-Ln-C bond, interactions
between the metal center and the alkenyl moiety are
assumed, which cause insertion of the vinylic group into
the σ-Ln-C bond. In the case of the divalent samarium
complex, the steric conditions at the double bond
prevented autocatalytic decomposition reactions. Bis-
(cyclopentadienyl)lanthanidocenes with unsubstituted
vinyl side chains at the cyclopentadienyl ligands reacted
regioselectively with 9-BBN, forming stable complexes.
These first hydroborations of lanthanidocenes demon-
strate the potential of (alkenylcyclopentadienyl)lan-
thanide complexes in further functionalization.
Ack n ow led gm en t. This work was supported by the
Fonds der Chemischen Industrie and the Deutsche
Forschungsgemeinschaft (Graduiertenkolleg “Synthe-
tische, mechanistische und reaktionstechnische Aspekte
von Metallkatalysatoren”).
Su p p or tin g In for m a tion Ava ila ble: Full details of the
X-ray structural analyses of 2a , 3, 5b, 7, and 12, including
tables of crystal data, atomic coordinates, bond lengths and
angles, and thermal parameters. This material is available free
of charge via the Internet at http://pubs.acs.org.
OM020654B