Reaction of zirconocene-carboryne precursor with alkynes: An efficient route to zirconacyclopentenes incorporating a carboranyl unit

Article abstract of DOI:10.1021/om9002973

Reaction of zirconocene-carboryne precursor Cp₂Zr(μ-Cl)(μ- C₂B₁₀H₁₀)Li(OEt₂)₂ with various kinds of alkynes R¹C=CR² in refluxing toluene gives the monoinsertion produc

Full text of DOI:10.1021/om9002973

4106 Organometallics 2009, 28, 4106–4114
DOI: 10.1021/om9002973
Reaction of Zirconocene-Carboryne Precursor with Alkynes: An
Efficient Route to Zirconacyclopentenes Incorporating a Carboranyl Unit
Shikuo Ren,† Hoi-Shan Chan,† and Zuowei Xie*,†,‡
†Department of Chemistry, The Chinese University of Hong Kong, Shatin, New Territories,
Hong Kong, People’s Republic of China, and ‡State Key Laboratory of Elemento-Organic
Chemistry, Nankai University, Tianjin, People’s Republic of China
Received April 21, 2009
Reaction of zirconocene-carboryne precursor Cp2Zr(μ-Cl)(μ-C2B10H10)Li(OEt2)2 with various
kinds of alkynes R1CtCR2 in refluxing toluene gives the monoinsertion products 1,2-[Cp2ZrC(R1)-
dC(R2)]-1,2-C2B10H10 in good to very high isolated yields with very good chemo- and regioselec-
tivity. This reaction offers an efficient route to zirconacyclopentenes incorporating a carboranyl unit,
a carborane version of zirconacyclopentadienes. All complexes have been fully characterized by
various spectroscopic techniques and single-crystal X-ray analyses.
Introduction
(η3-C2B10H10)][Li(THF)4]6 shows that the bonding interac-
tions between Zr atom and carboryne resemble those
in the zirconocene-benzyne complex Cp2Zr(η2-C6H4)-
(PMe3) (Chart 1).3c This result prompted us to prepare
the corresponding zirconocene-carboryne Cp2Zr(η2-
C2B10H10). Unexpectedly, only Cp2Zr(μ-Cl)(μ-C2B10-
H10)Li(OEt2)2 (1) was isolated from the reaction of Cp2ZrCl2
with Li2C2B10H10. Subsequent reactivity studies prove 1 to
be a precursor of Cp2Zr(η2-C2B10H10).5a Very recently we
discovered that 1 can react with EtCtCEt to give 1,2-
[Cp2ZrC(Et)dC(Et)]-1,2-C2B10H10, which is a very useful
intermediate for the synthesis of a variety of functional
carboranes.7 In this connection, we explored the generality
of the reaction of 1 with various kinds of alkynes. This
article reports the synthesis and structural characterization
of a new class of zirconacyclopentenes incorporating a
carboranyl unit.
Zirconacyclopentadienes/zirconaindenes are very use-
ful reagents in various organic transformations, and their
chemistry has been extensively explored.1 These com-
plexes are commonly prepared by an oxidative coupling
of two alkynes2 or one alkyne and one benzyne3 on divalent
zirconocene Cp2Zr(II). In view of the similar reactivity
patterns between benzyne and carboryne (1,2-dehydro-1,2-
carborane),4 we initiated a research program to study the
chemistry of metal-carboryne complexes5 and to develop
a carborane version of zirconacyclopentadiene reagents.
Our previous work on [{η5:σ-Me2C(C9H6)(C2B10H10)}ZrCl-
*Corresponding author. E-mail: zxie@cuhk.edu.hk.
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Results and Discussion
Reaction with Symmetrical Alkynes. Treatment of Cp2Zr-
(μ-Cl)(μ-C2B10H10)Li(OEt2)2 (1) with 1.5-2 equiv of
RCtCR in refluxing toluene gave 1,2-[Cp2ZrC(R)dC(R)]-
~
ꢀ
Rev. 2007, 36, 1395. (h) Fananas, F. J.; Rodríguez, F. Eur. J. Org. Chem.
2008, 1315.
n
n
1,2-C2B10H10 (3) (R=Et (3a), Pr (3b), Bu (3c), Ph (3d))
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pubs.acs.org/Organometallics
Published on Web 06/25/2009
2009 American Chemical Society

Article
Organometallics, Vol. 28, No. 14, 2009 4107
Chart 1. Bonding Description
Scheme 1
as yellow crystals in 65-93% isolated yields (Scheme 1).
No double-insertion products were observed. An excess
amount of alkynes was used to ensure the full conversion
of 1, facilitating the isolation of the products. Both solvents
and temperatures are crucial to this reaction. Complexes 3a-
d were not observed if donor solvents such as Et2O and THF
were used instead of toluene, suggesting that the coordina-
tion of alkyne to the Zr atom is essential for the subsequent
insertion. High temperature is required, as it not only can
promote the dissociation of LiCl from 1 forming the zirco-
nocene-carboryne intermediate but may also facilitate the
coupling reaction between carboryne and the coordinated
alkyne via the intermediate A (Scheme 1). It is noted that
sterically demanding alkyne Me3SiCtCSiMe3 did not react
with 1 even after prolonged heating in toluene.8 PhCtCPh
offered a much lower yield (65%) than linear alkynes (80-
93%). The very bulkyl icosahedral carboranyl moiety may
play a role in these insertion reactions because of steric
reasons.
The most characteristic vinyl carbons in the products 3a-
d were observed at about 195 and 144 ppm in their 13C NMR
spectra, which are very comparable to the corresponding
values of ∼194 and ∼142 ppm observed in Cp2Zr[C(R)dC-
(R)]2.9 Two distinct cage carbons were found at ∼92 and ∼90
ppm, respectively, in the 13C NMR spectra. The unique Cp
carbons at ∼115 ppm and protons at ∼6.6 ppm as a singlet
were also observed. The 11B NMR spectra exhibited different
patterns, a 1:3:2:2:2 for 3a, a 1:2:3:4 for 3b and 3c, and a
2:3:3:2 for 3d in the range 0-11 ppm.
regioselectivity (Table 1, entry 7). For linear alkynes such as
nPrCtCCH3, both regioisomers were observed in about 1:1
ratio, resulting in an inseparable mixture. Alkynes contain-
ing functional groups such as 4d,h,l,m often offered relatively
low isolated yields due to unknown side reactions, although
the conversion of 1 is 100%. Terminal alkynes such as
PhCtCH are not compatible with the above reactions, as
they can protonate 1 to generate o-carborane.
Complexes 3a-d and 5a-m are very soluble in donor
solvents, but are insoluble in hexane. Complexes 3b,c and
5f,m are soluble in hot aromatic solvents, whereas 3a,d
and 5a-e,g-l are only barely soluble. They are stable
in air for a few minutes in the solid state; however, their
solutions are moisture-sensitive. They were fully character-
ized by various spectroscopic techniques and elemen-
tal analyses. Two characteristic vinyl carbons in the range
140-211 ppm and two unique cage carbons at ∼90 ppm
were observed in their 13C NMR spectra. The Cp protons
displayed a singlet at ∼6.5 ppm in their 1H NMR spectra.
Structure. Molecular structures of 3a,c,d and 5a,c,d,f-m are
further confirmed by single-crystal X-ray analyses. Figures 1-13
show the representative structures. Selected bond distances
and angles are summarized in Tables 2 and 3, respectively.
Except for 5i (Figure 9), in which an additional coordina-
tion bond between the Zr and P atoms with the Zr-P distance
Reaction with Unsymmetrical Alkynes. In a very similar
manner, reaction of 1 with 1.5-2 equiv of unsymmetrical
alkynes 4 in refluxing toluene afforded the monoinser-
tion products 5a-m in yields of 35-88%. The results are
summarized in Table 1. The regioselectivity of these reac-
tions may be best ascribed to the polarity of alkynes, as
phenyl is often considered an electron-withdrawing group.10
In the case of 4g, steric factors may also play a role in the
˚
of 2.787(3) A is observed, all other complexes adopt a distorted-
(8) It was reported that reaction of Cs[3,30-Co(8-I-1,2-C2B9H10)-
tetrahedral coordination environment. As shown in Table 2, the
Zr-C(1) distance of 2.507(3) A in 5i is much longer than those
(10,20-C2B9H11)] with TMSCtCH gave Cs[μ-8,80-C2H2-3,30-Co(1,2-
˚
€
C2B9H10)2]; see: Rojo, I.; Teixidor, F.; Kivekas, R.; Sillanpaa, R.;
€€
˚
(2.378(4)-2.406(2) A) observed in its analogues, while the Zr-
C(4) distance of 2.265(3) A in 5i is shorter than the corresponding
~
Vinas, C. J. Am. Chem. Soc. 2003, 125, 14720.
˚
(9) For examples, see: (a) Jones, S. B.; Peterson, J. L. Organometallics
1985, 4, 966. (b) Negishi, E.; Holmes, S. J.; Tour, J. M.; Miller, J. A.;
Cederbaum, F. E.; Swanson, D. R.; Takahashi, T. J. Am. Chem. Soc. 1989,
111, 3336. (c) Erker, G.; Zwettler, R.; Krueger, C.; Hyla-Kryspin, I.; Gleiter,
R. Organometallics 1990, 9, 524. (d) Mohamadi, F.; Spees, M. M. Organo-
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1995, 117, 7031. (f) Mao, S. S. H.; Liu, F.-Q.; Tilley, T. D. J. Am. Chem. Soc.
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2000, 19, 1806. (i) Schafer, L. L.; Tilley, T. D. J. Am. Chem. Soc. 2001, 123,
2683. (j) Johnson, S. A.; Liu, F.-Q.; Suh, M. C.; Z€urcher, S.; Haufe, M.; Mao,
S. S. H.; Tilley, T. D. J. Am. Chem. Soc. 2003, 125, 4199. (k) Hilton, C. L.;
King, B. T. Organometallics 2006, 25, 4058. (l) Miller, A. D.; McBee, J. L.;
Tilley, T. D. J. Am. Chem. Soc. 2008, 130, 4992. (m) Miller, A. D.; Tannaci,
J. F.; Johnson, S. A.; Lee, H.; McBee, J. L.; Tilley, T. D. J. Am. Chem. Soc.
2009, 131, 4917.
˚
values (2.277(2)-2.309(3) A) found in its analogues. Such
differences result from the additional coordination of the P to
˚
the Zr atom. The C(3)-C(4) distance of ca. 1.34 A and C(2)-
C(3) distance of ca. 1.51 A clearly suggest their double- and
˚
˚
single-bond characters. The C(1)-C(2) distance of ca. 1.68 A is a
typical value found in o-carboranes.11 The Zr-C(1) distances
(11) (a) Ren, S.; Xie, Z. Organometallics 2008, 27, 5167. (b) Xie, Z.
Acc. Chem. Res. 2003, 36, 1. (c) Xie, Z. Coord. Chem. Rev. 2002, 231, 23.
(d) Hosmane, N. S.; Maguire, J. A. In Comprehensive Organometallic
Chemistry III; Crabtree, R. H., Mingos, D. M. P., Eds.; Elsevier: Oxford,
2007; Vol. 3, p175. (e) Saxena, A. K.; Hosmane, N. S. Chem. Rev. 1993, 93,
~
(10) Bennett, M. A.; Macgregor, S. A.; Wenger, E. Helv. Chim. Acta
1081. (f) Oliva, J. M.; Allan, N. L.; Schleyer, P. V. R.; Vinas, C.; Teixidor, F. J.
2001, 84, 3084.
Am. Chem. Soc. 2005, 127, 13538.

4108 Organometallics, Vol. 28, No. 14, 2009
Ren et al.
Table 1. Reaction of 1 with Unsymmetrical Alkynes
Figure 2. Molecular structure of 1,2-[Cp2ZrC(Ph)dC(Ph)]-1,2-
C2B10H10 (3d) (thermal ellipsoids drawn at the 35% probability
level).
Figure 3. Molecular structure of 1,2-[Cp2ZrC(Ph)dC(Me)]-
1,2-C2B10H10 (5a) (thermal ellipsoids drawn at the 35% prob-
ability level).
˚
distances fall in the range 2.265(3)-2.309(3) A, which are very
close to the corresponding values found in zirconacyclopenta-
dienes.13 On the other hand, the sum of five interior angles on the
five-membered zirconacyclopentene ring is very close to 540°,
suggestive of a planar geometry. These structural features
resemble those of zirconacyclopentadienes.13
In summary, we have developed an efficient and practical
method to prepare a new class of zirconacyclopentenes
incorporating a carboranyl unit from the reaction of zirco-
nocene-carboryne precursor 1 with alkynes. This reaction
can tolerate many functional groups such as vinyl, chloro,
amido, alkoxyl, and tetrahydro-2-pyranyl. The resul-
tant zirconacycles are potential intermediates, which can
be converted to a variety of functionalized carboranes,
as evidenced by our preliminary results.7
Figure 1. Molecular structure of 1,2-[Cp2ZrC(Bun)dC(Bun)]-
1,2-C2B10H10 (3c) (thermal ellipsoids drawn at the 35% prob-
ability level).
˚
(2.378(4)-2.507(3) A) are very close to the corresponding values
observed in zirconocene-carboranyl complexes.12 The Zr-C(4)
(12) (a) Kang, S. O.; Ko, J. Adv. Organomet. Chem. 2001, 47, 61. (b)
Deng, L.; Xie, Z. Organometallics 2007, 26, 1832. (c) Deng, L.; Xie, Z.
Coord. Chem. Rev. 2007, 251, 2452. (d) Xie, Z. Coord. Chem. Rev. 2006,
250, 259.
(13) For examples, see refs 8a,c,e-g,i-m. and: (a) Hunter, W. E.;
Atwood, J. L.; Fachinetti, G.; Floriani, C. J. Organomet. Chem. 1981,
204, 67. (b) Nugent, W. A.; Thorn, D. L.; Harlow, R. L. J. Am. Chem. Soc.
1987, 109, 2788.

Article
Organometallics, Vol. 28, No. 14, 2009 4109
Figure 4. Molecular structure of 1,2-[Cp2ZrC(Ph)dC(Bun)]-
1,2-C2B10H10 (5c) (thermal ellipsoids drawn at the 35% pro-
bability level).
Figure 6. Molecular structure of 1,2-[Cp2ZrC(TMS)dC(Bun)]-
1,2-C2B10H10 (5f) (thermal ellipsoids drawn at the 35% pro-
bability level).
Figure 7. Molecular structure of 1,2-[Cp2ZrC(TMS)dC(Ph)]-
1,2-C2B10H10 (5g) (thermal ellipsoids drawn at the 35% pro-
bability level).
Figure 5. Molecular structure of 1,2-[Cp2ZrC(Ph)dC(CtC-
Ph)]-1,2-C2B10H10 (5d) (thermal ellipsoids drawn at the 35%
probability level).
Infrared spectra were obtained from KBr pellets prepared in
the glovebox on a Perkin-Elmer 1600 Fourier transform spec-
trometer. Elemental analyses were performed by the Shanghai
Institute of Organic Chemistry, CAS, China. Complex 15a
and alkynes of 4d,14a 4e,14b 4f,14c 4g,14d 4i,14e 4j,14f 4k,14g 4l,14h
and 4m14i,14j were prepared according to the literature methods.
All other chemicals were purchased from either Aldrich
or Acros Chemical Co. and used as received unless otherwise
specified.
Experimental Section
General Procedures. All reactions were performed under an
atmosphere of dry nitrogen with the rigid exclusion of air and
moisture using standard Schlenk or cannula techniques, or in
a glovebox. 1H NMR spectra were recorded on either a Bruker
DPX 300 spectrometer at 300 MHz or a Bruker DPX 400
spectrometer at 400 MHz. 13C{1H} NMR spectra were recorded
on either a Bruker DPX 300 spectrometer at 75 MHz or a Bruker
DPX 400 spectrometer at 100 MHz. 11B{1H} NMR spectra were
recorded on either a Bruker DPX 300 spectrometer at 96 MHz
or a Varian Inova 400 spectrometer at 128.3 MHz. 31P NMR
spectra were recorded on a Bruker DPX 300 spectrometer at
121 MHz. All chemical shifts were reported in δ units with
reference to the residual protons and carbons of the deutera-
ted solvents for proton and carbon chemical shifts, to exter-
Preparation of 1,2-[Cp2ZrC(Et)dC(Et)]-1,2-C2B10H10 (3a).
To a toluene solution (20 mL) of 1 (554 mg, 1.0 mmol) was
(14) (a) Li, D.; Yin, K.; Li, J.; Jia, X. Tetrahedron Lett. 2008, 49, 5918.
(b) Weiss, H. M.; Touchette, K. M.; Angell, S.; Khan, J. Org. Biomol. Chem.
2003, 1, 2152. (c) Bestmann, H. J.; Zeibig, T.; Vostrowsky, O. Synthesis 1990,
1039. (d) Page, P. C. B.; Rosenthal, S. Tetrahedron 1990, 46, 2573. (e) Xi, Z.;
Zhang, W.; Takahashi, T. Tetrahedron Lett. 2004, 45, 2427. (f) Baker, M. V.;
Brown, D. H.; Skelton, B. W.; White, A. H. Dalton. Trans. 2000, 4607. (g)
Bieber, L. W.; Silva, M. F. Tetrahedron Lett. 2004, 45, 8281. (h) Roesch, K.
R.; Larock, R. C. J. Org. Chem. 2001, 66, 412. (i) Zheng, T.; Narayan, R. S.;
Schomaker, J. M.;Borhan, B. J. Am. Chem. Soc. 2005, 127, 6946. (j) Bernady,
K. F.; Floyd, M. B.; Poletto, J. F.; Weiss, M. J. J. Org. Chem. 1979, 44, 1438.
nal BF3 OEt2 (0.00 ppm) for boron chemical shifts, and to
external 85% H3PO4 (0.00 ppm) for phosphorus chemical shifts.
3

4110 Organometallics, Vol. 28, No. 14, 2009
Ren et al.
Figure 10. Molecular structure of 1,2-[Cp2ZrC(Ph)dC((CH2)3-
Cl)]-1,2-C2B10H10 (5j) (thermal ellipsoids drawn at the 35%
probability level).
Figure 8. Molecular structure of 1,2-[Cp2ZrC((CdCH2)Me)-
dC(Et)]-1,2-C2B10H10 (5h) (thermal ellipsoids drawn at the
35% probability level).
Figure 11. Molecular structure of 1,2-[Cp2ZrC(Ph)dC(N-
(CH3)2)]-1,2-C2B10H10 (5k) (thermal ellipsoids drawn at the
35% probability level).
Figure 9. Molecular structure of 1,2-[Cp2ZrC(PPh2)dC(Bun)]-
1,2-C2B10H10 (5i) (thermal ellipsoids drawn at the 35% prob-
ability level).
added 3-hexyne (2a) (164 mg, 2.0 mmol), and the reaction
mixture was heated to reflux for 48 h. After removal of
the precipitate (LiCl), the clear solution was concentrated
to about 5 mL, from which 3a was isolated as yellow
crystals after standing at room temperature overnight (415 mg,
93%). 1H NMR (300 MHz, pyridine-d5): δ 6.57 (s, 10H, C5H5),
2.17 (q, J=7.5 Hz, 2H, CH2), 1.30 (q, J=7.5 Hz, 2H, CH2),
1.13 (t, J=7.5 Hz, 3H, CH3), 0.81 (t, J=7.5 Hz, 3H, CH3). 13
C
{1H} NMR (100 MHz, pyridine-d5): δ 195.1, 144.1 (olefinic),
115.8 (Cp), 91.7, 87.1 (cage C), 25.7, 22.1, 13.4, 13.0 (Et). 11B{1H}
NMR (128 MHz, pyridine-d5): δ -0.8 (1B), -5.1 (3B), -7.5 (2B),
-9.1 (2B), -10.0 (2B). IR (KBr, cm-1): ν 2572 (B-H). Anal.
Calcd for C18H30B10Zr (3a): C, 48.50; H, 6.78. Found: C, 48.25;
H, 6.60.
Preparation of 1,2-[Cp2ZrC(Prn)dC(Prn)]-1,2-C2B10H10 (3b).
This complex was prepared as yellow crystals from 1 (554 mg,
1.0 mmol) and 4-octyne (2b) (220 mg, 2.0 mmol) using the same
procedures reported for 3a: yield 379 mg (80%). 1H NMR (400
MHz, benzene-d6): δ 5.88 (s, 10H, C5H5), 2.08 (m, 2H, CH2),
1.57 (m, 2H, CH2), 0.95 (m, 4H, CH2), 0.92 (t, J=7.2 Hz, 3H,
Figure 12. Molecular structure of 1,2-[Cp2ZrC(Ph)dC-
(CH2OCH)]-1,2-C2B10H10 (5l) (thermal ellipsoids drawn at the
35% probability level).

Article
Organometallics, Vol. 28, No. 14, 2009 4111
CH3), 0.77 (t, J = 5.6 Hz, 3H, CH3). 13C{1H} NMR (100
MHz, benzene-d6): δ 193.2, 144.7 (olefinic), 115.9 (Cp), 91.7,
87.1 (cage C), 36.2, 33.6, 22.9, 22.8 (CH2), 15.3, 14.8 (CH3).
11B{1H} NMR (128 MHz, benzene-d6): δ 0.1 (1B), -4.7 (2B), -
7.1 (3B), -9.2 (4B). IR (KBr, cm-1): ν 2562 (B-H). Anal.
Calcd for C20H34B10Zr (3b): C, 50.70; H, 7.23. Found:
C, 50.58; H, 7.16.
NMR (300 MHz, pyridine-d5): δ 7.22 (dd, J=7.2 Hz, 4H, C6H5),
7.12 (d, J = 7.2 Hz, 2H, C6H5), 7.04 (d, J = 7.2 Hz, 2H,
C6H5), 6.90 (dd, J=7.2 Hz, 1H, C6H5), 6.80 (dd, J=7.2 Hz,
1H, C6H5), 6.33 (s, 10H, C5H5). 13C{1H} NMR (75 MHz,
pyridine-d5): δ 194.8, 153.6 (olefinic), 143.0, 140.0, 131.0,
126.8, 126.2, 126.1, 124.7, 122.1 (C6H5), 112.2 (Cp), 94.2,
90.3 (cage C). 11B{1H} NMR (128 MHz, pyridine-d5): δ -2.8
(2B), -5.5 (3B), -8.7 (3B), -11.0 (2B). IR (KBr, cm-1): ν 2564
(B-H). Anal. Calcd for C26H30B10Zr (3d): C, 57.63; H, 5.58.
Found: C, 57.65; H, 5.60.
Preparation of 1,2-[Cp2ZrC(Ph)dC(Me)]-1,2-C2B10H10 (5a).
This complex was prepared as orange crystals from 1 (554 mg,
1.0 mmol) and PhCtCMe (4a) (174 mg, 1.5 mmol) using the
same procedures reported for 3a: yield 432 mg (90%). 1H NMR
(300 MHz, pyridine-d5): δ 7.35 (dd, J=7.5 Hz, 2H, C6H5), 7.14
(dd, J=7.5 Hz, 1H, C6H5), 6.93 (d, J=7.2 Hz, 2H, C6H5), 6.54 (s,
10H, C5H5), 1.56 (s, 3H, CH3). 13C{1H} NMR (100 MHz,
pyridine-d5): δ 193.6, 144.8 (olefinic), 137.5, 128.2, 126.0,
124.1 (C6H5), 116.9 (Cp), 91.1, 87.9 (cage C), 20.3 (CH3).
11B{1H} NMR (128 MHz, pyridine-d5): δ -0.5 (1B), -5.0
(2B), -7.4 (3B), -8.8 (2B), -10.0 (2B). IR (KBr, cm-1):
ν 2638, 2559 (B-H). Anal. Calcd for C21H28B10Zr (5a):
C, 52.57; H, 5.88. Found: C, 52.56; H, 5.87.
Preparation of 1,2-[Cp2ZrC(Bun)dC(Bun)]-1,2-C2B10H10 (3c).
This complex was prepared as yellow crystals from 1 (554 mg,
1.0 mmol) and 5-decyne (2c) (207 mg, 1.5 mmol) using
1
the same procedures reported for 3a: yield 407 mg (81%). H
NMR (300 MHz, benzene-d6): δ 5.88 (s, 10H, C5H5), 2.16 (m,
2H, CH2), 1.62 (m, 2H, CH2), 1.35 (m, 2H, CH2), 1.16 (m, 2H,
CH2), 1.02 (m, 4H, CH2), 0.96 (t, J=7.5 Hz, 3H, CH3), 0.87 (t,
J=7.5 Hz, 3H, CH3). 13C{1H} NMR (100 MHz, benzene-d6):
δ 193.3, 145.1 (olefinic), 116.2 (Cp), 92.0, 87.5 (cage C), 34.1,
32.0, 31.2, 24.4, 24.0 (CH2), 14.5, 14.4 (CH3). 11B{1H} NMR (128
MHz, benzene-d6): δ 0.0 (1B), -4.6 (2B), -7.1 (3B), -9.2 (4B).
IR (KBr, cm-1): ν 2635, 2562 (B-H). Anal. Calcd for
C22H38B10Zr (3c): C, 52.65; H, 7.63. Found: C, 52.33; H, 7.52.
Preparation of 1,2-[Cp2ZrC(Ph)dC(Ph)]-1,2-C2B10H10 (3d).
This complex was prepared as yellow crystals from 1 (554 mg,
1.0 mmol) and PhCtCPh (2d) (267 mg, 1.5 mmol) using
1
the same procedures reported for 3a: yield 352 mg (65%). H
Preparation of 1,2-[Cp2ZrC(Ph)dC(Et)]-1,2-C2B10H10 (5b).
This complex was prepared as orange crystals from 1 (554 mg,
1.0 mmol) and PhCtCEt (4b) (195 mg, 1.5 mmol) using the
same procedures reported for 3a: yield 435 mg (88%). 1H NMR
(400 MHz, pyridine-d5): δ 7.36 (m, 4H, C6H5), 7.14 (dd, J=
7.2 Hz, 1H, C6H5), 6.25 (s, 10H, C5H5), 2.22 (q, J=7.2 Hz, 2H,
CH2), 1.05 (t, J=7.2 Hz, 3H, CH3. 13C{1H} NMR (100 MHz,
pyridine-d5): δ 192.1, 153.2 (olefinic), 139.3, 133.3 128.3, 127.0,
126.3 (C6H5), 112.4 (Cp), 94.1, 91.6 (cage C), 26.3 (CH2), 14.9
(CH3). 11B{1H} NMR (96 MHz, pyridine-d5): δ -2.1 (2B), -4.7
(3B), -8.3 (3B), -10.2 (2B). IR (KBr, cm-1): ν 2637, 2558
(B-H). Anal. Calcd for C22H30B10Zr (5b): C, 53.51; H, 6.12.
Found: C, 53.03; H, 6.21.
Preparation of 1,2-[Cp2ZrC(Ph)dC(Bun)]-1,2-C2B10H10 (5c).
This complex was prepared as orange crystals from 1 (554 mg,
1.0 mmol) and PhCtCBun (4c) (237 mg, 1.5 mmol) using the
same procedures reported for 3a: yield 397 mg (76%). 1H NMR
(300 MHz, pyridine-d5): δ 7.34 (dd, J=7.5 Hz, 2H, C6H5), 7.11
(dd, J=7.5 Hz, 1H, C6H5), 7.00 (d, J=7.5 Hz, 2H, C6H5), 6.54 (s,
10H, C5H5), 2.04 (m, 2H), 1.47 (m, 2H), 1.00 (m, 2H, CH2), 0.66
Figure 13. Molecular structure of 1,2-{Cp2ZrC(Ph)dC-
[(CH2)3O(tetrahydro-2-pyranyl)]}-1,2-C2B10H10 (5m) (thermal
ellipsoids drawn at the 35% probability level).
˚
Table 2. Selected Bond Lengths (A)
compd
av Zr-Centa
av Zr-C (Cp ring)
Zr-C(1)
C(1)-C(2)
C(2)-C(3)
C(3)-C(4)
Zr-C(4)
3a
3c
3d
5a
5c
5d
5f
5g
5h
5i
2.218
2.214
2.208
2.211
2.213
2.204
2.226
2.232
2.217
2.229
2.209
2.209
2.219
2.211
2.516(2)
2.508(3)
2.506(3)
2.512(3)
2.514(4)
2.503(4)
2.524(3)
2.519(3)
2.516(3)
2.526(3)
2.507(4)
2.511(4)
2.515(3)
2.509(4)
2.390(2)
2.386(2)
2.391(2)
2.384(3)
2.376(4)
2.385(4)
2.382(2)
2.394(3)
2.406(2)
2.507(3)
2.378(4)
2.382(3)
2.395(3)
2.385(4)
1.680(3)
1.688(4)
1.680(3)
1.684(4)
1.695(5)
1.680(5)
1.684(3)
1.678(3)
1.689(3)
1.721(4)
1.684(5)
1.695(5)
1.689(4)
1.684(5)
1.510(3)
1.515(4)
1.514(3)
1.509(4)
1.519(6)
1.514(5)
1.531(3)
1.524(4)
1.505(3)
1.505(4)
1.515(5)
1.512(5)
1.513(4)
1.509(5)
1.346(3)
1.344(3)
1.342(3)
1.334(4)
1.330(6)
1.349(5)
1.350(3)
1.353(4)
1.341(3)
1.332(4)
1.337(5)
1.338(5)
1.338(4)
1.345(5)
2.277(2)
2.289(3)
2.288(2)
2.298(3)
2.296(4)
2.303(4)
2.299(2)
2.309(3)
2.291(2)
2.265(3)
2.299(4)
2.302(4)
2.309(3)
2.297(4)
5j
5k
5l
5m
a Cent = the centroid of Cp ring.

4112 Organometallics, Vol. 28, No. 14, 2009
Ren et al.
Table 3. Selected Bond Angles (deg)
compd
Cent-Zr-Cent
C(1)-Zr-C(4)
Zr-C(1)-C(2)
C(1)-C(2)-C(3)
C(2)-C(3)-C(4)
C(3)-C(4)-Zr
3a
3c
3d
5a
5c
5d
5f
5g
5h
5i
129.9
129.6
130.3
130.2
130.6
130.2
128.8
129.2
129.3
128.1
129.9
130.3
130.7
130.6
75.9(1)
76.1(1)
75.7(1)
75.5(1)
75.6(2)
76.5(1)
76.7(1)
77.4(1)
74.5(1)
69.0(1)
75.4(1)
74.8(1)
75.4(1)
75.5(1)
109.3(1)
109.1(1)
109.8(1)
109.6(2)
109.9(2)
109.5(2)
109.2(1)
108.9(2)
110.1(1)
111.5(2)
110.2(2)
110.6(2)
109.7 (2)
109.6(2)
113.6(2)
113.8(2)
113.0(2)
113.6(2)
113.0(3)
113.3(3)
113.4(2)
113.2(1)
113.2(2)
111.3(2)
113.1(3)
112.7(3)
113.5(2)
114.1(3)
119.6(2)
119.3(2)
120.3(2)
119.5(2)
119.3(4)
121.2(3)
119.9(2)
122.4(2)
118.8(2)
114.4(3)
119.6(3)
119.2(3)
119.7(3)
118.9(3)
121.6(2)
121.4(2)
121.3(1)
121.7(2)
122.1(3)
119.4(3)
119.6(2)
117.6(2)
123.4(2)
132.9(2)
121.7(3)
122.5(3)
121.7(2)
122.0(3)
5j
5k
5l
5m
(t, J=7.5 Hz, 3H, CH3). 13C{1H} NMR (100 MHz, pyridine-d5):
δ 194.9, 143.9 (olefinic), 143.5, 127.9, 126.2, 124.0 (C6H5),
117.0 (Cp), 91.6, 87.6 (cage C), 33.9, 32.0, 22.5 (CH2), 13.0
(CH3). 11B{1H} NMR (128 MHz, pyridine-d5): δ -0.5 (1B), -
5.0 (2B), -7.2 (3B), -8.8 (4B). IR (KBr, cm-1): ν 2557 (B-H).
Anal. Calcd for C24H34B10Zr (5c): C, 55.24; H, 6.57. Found: C,
55.00; H, 6.46.
Preparation of 1,2-[Cp2ZrC(Ph)dC(CtCPh)]-1,2-C2B10H10
(5d). This complex was prepared as orange crystals from 1
(554 mg, 1.0 mmol) and PhCtC-CtCPh (4d) (303 mg, 1.5
mmol) using the same procedures reported for 3a: yield 311 mg
(55%). 1H NMR (300 MHz, pyridine-d5): δ 7.40 (m, 2H,
C6H5), 7.22 (m, 8H, C6H5), 6.50 (s, 10H, C5H5). 13C{1H}
NMR (75 MHz, pyridine-d5): δ 210.8, 148.2 (olefinic),
130.9, 128.7, 128.0, 127.7, 127.5, 125.5, 124.5, 124.2, 123.5
(C6H5), 115.9 (Cp), 91.3, 89.5 (cage C), 87.7, 87.5 (-CtC-).
11B{1H} NMR (128 MHz, pyridine-d5): δ -0.7 (2B), -5.0
(3B), -7.3 (5B). IR (KBr, cm-1): ν 2568 (B-H). Anal. Calcd
for C28H30B10Zr (5d): C, 59.43; H, 5.34. Found: C, 59.57;
H, 5.48.
Preparation of 1,2-[Cp2ZrC(TMS)dC(Ph)]-1,2-C2B10H10
(5g). This complex was prepared as yellow crystals from 1 (554
mg, 1.0 mmol) and (TMS)CtCPh (4g) (261 mg, 1.5 mmol) using
1
the same procedures reported for 3a: yield 269 mg (50%). H
NMR (300 MHz, pyridine-d5): δ 7.30 (m, 5H, C6H5), 6.69 (s,
10H, C5H5), -0.22 (s, 9H, TMS). 13C{1H} NMR (100 MHz,
pyridine-d5): δ 205.4, 153.9 (olefinic), 143.2, 130.7, 126.5, 126.4
(C6H5), 115.8 (Cp), 93.3, 87.6 (cage C), 3.3 (TMS). 11B{1H}
NMR (96 MHz, pyridine-d5): δ -1.0 (2B), -4.4 (3B), -7.5 (5B).
IR (KBr, cm-1): ν 2561 (B-H). Anal. Calcd for C23H34B10SiZr
(5g): C, 51.35; H, 6.37. Found: C, 51.36; H, 6.46.
Preparation of 1,2-{Cp2ZrC[C(CH3)dCH2]dC(Et)}-1,2-
C2B10H10 (5h). This complex was prepared as brown crystals
from 1 (554 mg, 1.0 mmol) and CH2dC(CH3)-CtCEt (4h)
(188 mg, 2.0 mmol) using the same procedures reported for 3a:
1
yield 211 mg (46%). H NMR (300 MHz, pyridine-d5): δ 6.26
(s, 10H, C5H5), 4.11 (s, 1H, dCH2), 3.61 (s, 1H, dCH2), 2.26 (q,
J=7.4 Hz, 2H, CH2), 1.81 (s, 3H, CH3), 1.08 (t, J=7.4 Hz, 3H,
CH3). The 13C NMR spectrum was not obtained due to the poor
solubility. 11B{1H} NMR (96 MHz, pyridine-d5): δ -0.5 (2B),
-4.9 (3B), -6.4 (3B), -10.3 (2B). IR (KBr, cm-1): ν 2627, 2565
(B-H). Anal. Calcd for C19H30B10Zr (5h): C, 49.85; H, 6.61
Found: C, 49.69; H, 6.57.
Preparation
of
1,2-[Cp2ZrC(4-CH3C6H4)dC(Me)]-1,2-
C2B10H10 (5e). This complex was prepared as brown crystals
from 1 (554 mg, 1.0 mmol) and (4-CH3C6H4)CtCMe (4e) (195
mg, 1.5 mmol) using the same procedures reported for 3a: yield
336 mg (68%). 1H NMR (300 MHz, pyridine-d5): δ 7.19 (m, 4H,
C6H4), 6.23 (s, 10H, C5H5), 2.31 (s, 3H, CH3), 1.76 (s, 3H, CH3).
13C{1H} NMR (100 MHz, pyridine-d5): δ 191.3, 152.8 (olefinic),
131.8, 131.2, 128.0, 127.9, 125.9 (C6H5), 111.6 (Cp), 95.9, 91.6
(cage C), 20.3 (CH3). 11B{1H} NMR (96 MHz, pyridine-d5):
δ -2.5 (2B), -5.1 (3B), -8.7 (3B), -10.0 (2B). IR (KBr, cm-1):
ν 2638, 2555 (B-H). Anal. Calcd for C22H30B10Zr (5e): C, 53.51;
H, 6.12. Found: C, 53.75; H, 6.11.
Preparation of 1,2-[Cp2ZrC(PPh2)dC(Bun)]-1,2-C2B10H10
(5i). This complex was prepared as yellow crystals from 1
(554 mg, 1.0 mmol) and Ph2PCtCBun (4i) (399 mg, 1.5 mmol)
using the same procedures reported for 3a: yield 473 mg (76%).
1H NMR (400 MHz, pyridine-d5): δ 7.72 (m, 4H, C6H5), 7.52
(m, 6H, C6H5), 5.99 (s, 10H, C5H5), 2.71 (m, 2H, CH2), 1.42 (m,
2H), 1.07 (m, 2H, CH2), 0.64 (t, J=8.0 Hz, 2H, CH3). 13C{1H}
NMR (100 MHz, pyridine-d5): δ 170.8, 164.7 (olefinic), 163.7,
132.7, 131.3, 130.0, 129.0 (C6H5), 108.4 (Cp), 99.7, 98.4 (cage C),
38.8, 30.7, 22.6 (CH2), 13.0 (CH3). 11B{1H} NMR (96 MHz,
pyridine-d5): δ -0.0 (2B), -4.3 (6B), -9.0 (2B). 31P{1H} NMR
(121 MHz, pyridine-d5): δ -66.7. IR (KBr, cm-1): ν 2558 (B-H).
Anal. Calcd for C30H39B10PZr (5i): C, 57.20; H, 6.24. Found:
C, 56.97; H, 6.38.
Preparation of 1,2-[Cp2ZrC(TMS)dC(Bun)]-1,2-C2B10H10
(5f). This complex was prepared as brown crystals from 1
(554 mg, 1.0 mmol) and TMSCtCBun (4f) (231 mg, 1.5 mmol)
using the same procedures reported for 3a: yield 451 mg (87%).
1H NMR (400 MHz, benzene-d6): δ 5.94 (s, 10H, C5H5), 2.23 (m,
2H, CH2), 1.71 (m, 2H, CH2), 1.29 (m, 2H, CH2), 0.93 (t, J=
7.3 Hz, 3H, CH3), -0.18 (s, 9H, TMS). 13C{1H} NMR (75 MHz,
benzene-d6): δ 205.3, 158.4 (olefinic), 116.9 (Cp), 93.7, 86.7 (cage
C), 41.0, 34.1, 23.7, 14.5 (Bun), 3.3 (TMS). 11B{1H} NMR
(96 MHz, benzene-d6): δ 0.1 (2B), -3.6 (2B), -6.8 (3B), -8.7
(3B). IR (KBr, cm-1): ν 2620, 2562 (B-H). Anal. Calcd for
C21H38B10SiZr (5f): C, 48.70; H, 7.40. Found: C, 49.02; H, 7.51.
Preparation of 1,2-{Cp2ZrC(Ph)dC[(CH2)3Cl]}-1,2-C2B10-
H10 (5j). This complex was prepared as brown crystals from
1 (554 mg, 1.0 mmol) and PhCtC(CH2)3Cl (4j) (268 mg,
1.5 mmol) using the same procedures reported for 3a: yield
1
482 mg (89%). H NMR (300 MHz, pyridine-d5): δ 7.34 (dd,
J=7.2 Hz, 2H, C6H5), 7.12 (dd, J=7.2 Hz, 1H, C6H5), 6.99
(d, J=7.2 Hz, 2H, C6H5), 6.52 (s, 10H, C5H5), 3.25 (t, J=6.8 Hz,

Article
Organometallics, Vol. 28, No. 14, 2009 4113
Table 4. Crystal Data and Summary of Data Collection and Refinement for 3a, 3c, 3d, 5a, 5c, 5d, and 5f
3a
3c
3d
5a
5c
5d 1.5C7H8
5f
3
formula
cryst size, mm
C18H30B10Zr
0.40 ꢀ 0.30 ꢀ
0.20
C22H38B10Zr
0.40 ꢀ 0.4 ꢀ
0.30
C26H30B10Zr
0.40 ꢀ 0.4 ꢀ
0.30
C21H28B10Zr
0.40 ꢀ 0.30 ꢀ
0.20
C24H34B10Zr
0.50 ꢀ 0.40 ꢀ
0.30
C38.50H42B10Zr
0.40 ꢀ 0.40 ꢀ
0.30
C21H38B10SiZr
0.40 ꢀ 0.40 ꢀ
0.30
fw
cryst syst
445.74
monoclinic
C2/c
501.84
monoclinic
P21/c
541.82
monoclinic
P21/n
479.75
triclinic
P1
521.83
tetragonal
P4/n
704.04
triclinic
P1
517.92
monoclinic
P21/n
space group
˚
a, A
26.251(2)
9.445(1)
18.280(2)
90
15.956(3)
8.313(1)
20.484(3)
90
8.264(1)
19.753(3)
16.705(3)
90
8.938(2)
10.478(2)
13.004(2)
91.02(1)
102.78(1)
93.48(1)
1185.0(4)
2
23.044(1)
23.044(1)
10.426(1)
90
11.137(3)
12.012(3)
14.742(3)
83.26(1)
88.17(1)
71.80(1)
1860.5(7)
2
15.400(1)
9.770(2)
19.293(4)
90
˚
b, A
˚
c, A
R, deg
β, deg
γ, deg
105.53(1)
90
100.94(1)
90
96.54(1)
90
90
90
110.00(1)
90
3
˚
V, A
Z
4366.9(6)
8
1.356
2667.8(8)
4
1.249
2709.4(8)
4
1.328
5536.8(3)
8
1.252
2727.6(9)
4
1.261
D
calcd, Mg/m3
1.345
1.257
˚
radiation (λ), A
Mo KR
(0.71073)
3.2 to 56.0
0.506
Mo KR
(0.71073)
4.0 to 56.0
0.422
Mo KR
(0.71073)
3.2 to 56.0
0.421
Mo KR
(0.71073)
3.2 to 56.2
0.472
Mo KR
(0.71073)
3.9 to 50.0
0.409
Mo KR
(0.71073)
2.8 to 56.2
0.323
Mo KR
(0.71073)
2.8 to 56.0
0.456
2θ range, deg
μ, mm-1
F(000)
1824
5280
1040
6413
1104
6527
488
5643
2144
4869
726
8859
1072
6565
no. of obsd reflns
no. of params refnd
goodness of fit
R1
262
1.048
298
1.056
334
1.023
289
1.038
316
1.184
460
1.017
298
1.038
0.031
0.078
0.039
0.100
0.039
0.100
0.045
0.110
0.053
0.155
0.0643
0.156
0.036
0.089
wR2
Table 5. Crystal Data and Summary of Data Collection and Refinement for 5g-m
5g
5h
5i
5j
5k
5l
5m 0.5C7H8
3
formula
cryst size, mm
C23H34B10SiZr
0.50 ꢀ 0.4 ꢀ
0.30
C19H30B10Zr
0.50 ꢀ 0.4 ꢀ
0.30
C30H39B10PZr
0.50 ꢀ 0.4 ꢀ
0.30
C23H31B10ClZr
0.40 ꢀ 0.30 ꢀ
0.20
C23H33B10NZr
0.40 ꢀ 0.30 ꢀ
0.20
C22H30B10OZr
0.50 ꢀ 0.40 ꢀ
0.30
C31.5H44B10O2Zr
0.40 ꢀ 0.30 ꢀ
0.20
fw
cryst syst
space group
537.91
triclinic
P1
457.75
monoclinic
C2/c
629.90
triclinic
P1
542.25
triclinic
P1
522.82
triclinic
P1
509.78
triclinic
P1
653.99
triclinic
P1
˚
a, A
10.244(1)
10.566(2)
14.281(2)
105.07(1)
100.16(1)
109.89(2)
1342.6(3)
2
26.326(4)
9.445(1)
18.317(3)
90
11.227(3)
11.761(3)
13.983(4)
67.01(1)
78.57(1)
74.34(1)
1627.6(8)
2
10.480(2)
10.630(2)
12.757(2)
74.93(1)
81.51(1)
76.40(1)
1328.1(3)
2
10.432(2)
14.015(2)
18.515(3)
90.89(1)
99.70(1)
96.73(1)
2648.2(7)
4
9.105(1)
10.434(1)
13.234(2)
91.46(1)
104.86(1)
92.93(1)
1212.6(3)
2
10.468(3)
13.040(4)
14.143(5)
91.38(1)
107.33(1)
91.20(1)
1841.7(10)
2
˚
b, A
˚
c, A
R, deg
β, deg
γ, deg
V, A
Z
102.69(1)
90
3
˚
4443.3(1)
8
1.369
D
calcd, Mg/m3
1.331
1.285
1.356
1.311
1.057
1.179
˚
radiation (λ), A
Mo KR
(0.71073)
3.1 to 56.1
0.467
Mo KR
(0.71073)
3.2 to 50.0
0.499
Mo KR
(0.71073)
3.2 to 50.0
0.407
Mo KR
(0.71073)
3.3 to 56.1
0.527
Mo KR
(0.71073)
2.2 to 56.0
0.429
Mo KR
(0.71073)
3.2 to 50.0
0.468
Mo KR
(0.71073)
3.0 to 50.0
0.325
2θ range, deg
μ, mm-1
F(000)
552
6359
1872
3913
648
5706
552
6295
1072
12 565
520
4247
678
6447
no. of obsd reflns
no. of params refnd
goodness of fit
R1
316
1.043
271
1.030
379
1.032
326
1.012
631
1.014
326
1.057
415
1.052
0.045
0.113
0.032
0.085
0.048
0.132
0.054
0.118
0.051
0.117
0.039
0.100
0.058
0.150
wR2
2H, CH2), 2.20 (m, 2H, CH2), 1.94 (m, 2H, CH2). 13C{1H}
NMR (75 MHz, pyridine-d5): δ 195.9, 144.2 (olefinic), 141.2,
128.0, 126.0, 124.1 (C6H5), 116.8 (Cp), 91.2, 87.8 (cage C), 44.5,
32.7, 31.6 (CH2). 11B{1H} NMR (128 MHz, pyridine-d5): δ -1.0
(1B), -5.5 (2B), -7.8 (3B), -10.0 (4B). IR (KBr, cm-1): ν 2557
(B-H). Anal. Calcd for C23H31B10ClZr (5j): C, 50.94; H, 5.76.
Found: C, 50.80; H, 6.02.
(s, 6H, CH3). 13C{1H} NMR (75 MHz, pyridine-d5): δ 199.1,
143.1 (olefinic), 139.7, 128.5, 127.7, 126.5 (C6H5), 116.7 (Cp),
91.6, 89.3 (cage C), 60.1 (CH2), 44.3 (CH3). 11B{1H} NMR
(96 MHz, pyridine-d5): δ -1.5 (1B), -5.7 (2B), -7.7 (3B), -10.1
(4B). IR (KBr, cm-1): ν 2628, 2558 (B-H). Anal. Calcd for
C23H33B10NZr (5k): C, 52.84; H, 6.36; N, 2.68. Found: C, 52.35;
H, 6.51; N, 2.58.
Preparation of 1,2-{Cp2ZrC(Ph)dC[CH2N(CH3)2]}-1,2-
C2B10H10 (5k). This complex was prepared as red crystals from
1 (554 mg, 1.0 mmol) and PhCtCCH2N(CH3)2 (4k) (239 mg,
1.5 mmol) using the same procedures reported for 3a: yield
408 mg (78%). 1H NMR (400 MHz, pyridine-d5): δ 7.32 (dd, J=
7.2 Hz, 2H, C6H5), 7.11 (dd, J=7.2 Hz, 1H, C6H5), 6.92 (d, J=
7.2 Hz, 2H, C6H5), 6.53 (s, 10H, C5H5), 2.84 (s, 2H, CH2), 1.99
Preparation of 1,2-[Cp2ZrC(Ph)dC(CH2OCH3)]-1,2-C2B10-
10 (5l). This complex was prepared as red crystals from 1 (554
H
mg, 1.0 mmol) and PhCtCCH2OCH3 (4l) (219 mg, 1.5 mmol)
using the same procedures reported for 3a: yield 188 mg (37%).
1H NMR (300 MHz, pyridine-d5): δ 7.43 (d, J=7.2 Hz, 2H), 7.35
(dd, J =7.2 Hz, 2H), 7.17 (dd, J=7.2 Hz, 1H) (C6H5), 6.20
(s, 10H, C5H5), 3.75 (s, 2H, CH2), 3.00 (s, 3H, CH3). 13C{1H}

4114 Organometallics, Vol. 28, No. 14, 2009
Ren et al.
NMR (75 MHz, pyridine-d5): δ 200.6, 153.7 (olefinic), 126.5,
126.0 (C6H5), 111.7 (Cp), 95.4, 90.4 (cage C), 71.4 (OCH2),
56.6 (CH3). 11B{1H} NMR (96 MHz, pyridine-d5): δ -3.1
(2B), -5.3 (2B), -8.5 (5B). IR (KBr, cm-1): ν 2630, 2559
(B-H). Anal. Calcd for C22H30B10OZr (5l): C, 51.83; H, 5.93.
Found: C, 51.66; H, 6.00.
X-ray Structure Determination. All single crystals were
immersed in Paraton-N oil and sealed under nitrogen in
thin-walled glass capillaries. Data were collected at 293 K
on a Bruker SMART 1000 CCD diffractometer using Mo KR
radiation. An empirical absorption correction was applied
using the SADABS program.15 All structures were solved
by direct methods and subsequent Fourier difference tech-
niques and refined anisotropically for all non-hydrogen
atoms by full-matrix least-squares on F2 using the SHEL-
XTL program package.16 Structures of 5d and 5m showed
1.5 and 1 toluene of solvation, respectively. All hydrogen
atoms were geometrically fixed using the riding model. Crystal
data and details of data collection and structure refinements
are given in Tables 4 and 5. Further details are included in
the Supporting Information.
Preparation of 1,2-{Cp2ZrC(Ph)dC[(CH2)3O(tetrahydro-2-
pyranyl)]}-1,2-C2B10H10 (5m). This complex was prepared as
pale red crystals from 1 (554 mg, 1.0 mmol) and PhCtC-
[(CH2)3O(tetrahydro-2-pyranyl)] (4m) (366 mg, 1.5 mmol) using
1
the same procedures reported for 3a: yield 197 mg (35%). H
NMR (400 MHz, benzene-d6): δ 7.01 (dd, J=7.2 Hz, 2H), 6.83
(dd, J=7.2 Hz, 1H), 6.53 (d, J=7.2 Hz, 2H) (C6H5), 5.83 (s, 10H,
C5H5), 4.41 (t, J=3.2 Hz, 1H, CH), 3.71 (m, 2H, CH2), 3.56 (m,
2H, CH2), 3.36 (m, 2H, CH2), 3.16 (m, 2H, CH2), 2.14 (m, 2H,
CH2), 1.77 (m, 2H, CH2), 1.51 (m, 2H, CH2), 1.25 (m, 2H, CH2).
13C{1H} NMR (100 MHz, benzene-d6): δ 194.5, 145.3 (olefinic),
144.5, 129.3, 126.7, 124.5 (C6H5), 116.8 (Cp), 98.0 (CO2), 91.7,
Acknowledgment. The work described in this paper was
supported by grants from the Research Grants Council of
the Hong Kong Special Administration Region (Project
No. 404108), The Chinese University of Hong Kong, and
the State Key Laboratory of Elemento-Organic Chemistry,
Nankai University (Project No. 0314).
87.8 (cage C), 66.9, 61.4, 31.7, 31.0, 30.9, 26.0, 19.5 (CH2). 11
B
{1H} NMR (96 MHz, benzene-d5): δ 0.5 (2B), -5.0 (2B), -6.6
(3B), -8.8 (3B). IR (KBr, cm-1): ν 2556 (B-H). Anal. Calcd for
C
C, 57.92; H, 6.97.
31.5H44B10O2Zr (5m þ 0.5toluene): C, 57.85; H, 6.78. Found:
(15) Sheldrick, G. M. SADABS: Program for Empirical Absorption
€
(16) Sheldrick, G. M. SHELXTL 5.10 for Windows NT: Structure
Determination Software Programs; Bruker Analytical X-ray Systems, Inc.:
Madison, WI, 1997.
Supporting Information Available: Crystallographic data
in CIF format for 3a, 3c, 3d, 5a, 5c, 5d, and 5f-m. This mate-
rial is available free of charge via the Internet at http://pubs.
acs.org.
Correction of Area Detector Data; University of Gottingen: Germany, 1996.