Synthesis, structural characterization, and reactivity of late transition-metal complexes bearing linked cyclopentadienyl-carboranyl ligands

Article abstract of DOI:10.1139/v11-115

Late transition-metal complexes bearing linked cyclopentadienyl/indenyl- carboranyl ligands were synthesized and their reactivities were examined. Reaction of Li₂[Me₂C(L)(C₂B₁₀H ₁₀)] (L = C₅H₄, C₉H₆, Me₂NCH₂CH₂C₅H₃) with MCl₂(PPh₃)₂ in Et₂O afforded [η⁵:σ-Me₂C(C₅H₄)(C ₂B₁₀H₁₀)]M(PPh₃) (M = Co (4), Ni (5)), [η⁵:σ-Me₂C(C₉H ₆)(C₂B₁₀H₁₀)]M(PPh₃) (M = Co (6), Ni (7)), and [η⁵:σ-Me₂C(Me ₂NCH₂CH₂C₅H₃)(C ₂B₁₀H₁₀)]Ni(PPh₃) (8). Treatment of 4 or 5 with 2,6-dimethylphenylisocyanide, N-heterocyclic carbene (NHC), PCy ₃, or 1,2-bis(diphenylphosphino)ethane (dppe) gave the corresponding PPh₃ displacement complexes [η⁵:σ-Me ₂C(C₅H₄)(C₂B₁₀H ₁₀)]M(2,6-Me₂C₆H₃NC) (M = Co (9), Ni (10)), [η⁵:σ-Me₂C(C₅H ₄)(C₂B₁₀H₁₀)]M[1,3-(2,6-i-Pr ₂C₆H₃)₂C₃N ₂H₂] (M = Co (11), Ni (12)), [η⁵:σ- Me₂C(C₅H₄)(C₂B₁₀H ₁₀)]Ni(PCy₃) (13), or {[η⁵:σ-Me ₂C(C₅H₄)(C₂B₁₀H ₁₀)]Co}₂(dppe) (14), respectively. These complexes were characterized by various spectroscopic techniques and elemental analyses. The molecular structures of 4-14 were further confirmed by single-crystal X-ray analyses.

Full text of DOI:10.1139/v11-115

108
Synthesis, structural characterization, and
reactivity of late transition-metal complexes
bearing linked cyclopentadienyl–carboranyl
ligands
Dongmei Liu, Zaozao Qiu, Hoi-Shan Chan, and Zuowei Xie
Abstract: Late transition-metal complexes bearing linked cyclopentadienyl/indenyl–carboranyl ligands were synthesized and
their reactivities were examined. Reaction of Li2[Me2C(L)(C2B10H10)] (L = C5H4, C9H6, Me2NCH2CH2C5H3) with MCl2(PPh3)2
in Et2O afforded [h5:s-Me2C(C5H4)(C2B10H10)]M(PPh3) (M = Co (4), Ni (5)), [h5:s-Me2C(C9H6)(C2B10H10)]M(PPh3)
(M = Co (6), Ni (7)), and [h5:s-Me2C(Me2NCH2CH2C5H3)(C2B10H10)]Ni(PPh3) (8). Treatment of 4 or 5 with 2,6-di-
methylphenylisocyanide, N-heterocyclic carbene (NHC), PCy3, or 1,2-bis(diphenylphosphino)ethane (dppe) gave the cor-
responding PPh3 displacement complexes [h5:s-Me2C(C5H4)(C2B10H10)]M(2,6-Me2C6H3NC) (M = Co (9), Ni (10)),
[h5:s-Me2C(C5H4)(C2B10H10)]M[1,3-(2,6-i-Pr2C6H3)2C3N2H2] (M = Co (11), Ni (12)), [h5:s-Me2C(C5H4)(C2B10H10)]Ni(PCy3)
(13), or {[h5:s-Me2C(C5H4)(C2B10H10)]Co}2(dppe) (14), respectively. These complexes were characterized by various
spectroscopic techniques and elemental analyses. The molecular structures of 4–14 were further confirmed by single-
crystal X-ray analyses.
Key words: carborane, cyclopentadienyl, cobalt complexes, nickel complexes, substitution reaction.
Résumé : On a effectué la synthèse de complexes de métaux de transition portant des ligands liés cyclopentadiényl/indényl-
carboranyles et on en a examiné les réactivités. La réaction du Li2[Me2C(L)(C2B10H10)] (L = C5H4, C9H6,
Me2NCH2CH2C5H3) avec le MCl2(PPh3)2, dans l’éther, conduit à la formation des [h5:s-Me2C(C5H4)(C2B10H10)]M(PPh3)
(M = Co (4); Ni (5)), [h5:s-Me2C(C9H6)(C2B10H10)]M(PPh3) (M = Co (6); Ni (7)) et [h5:s-Me2C(Me2NCH2CH2CH2C5H3)
(C2B10H10)]Ni(PPh3) (8). Le traitement des composés 4 et 5 avec de l’isocyanure de 2,6-diméthylphényle, des carbènes N-
hétérocycliques (NHC), du PCy3 ou du 1,2-bis(diphénylphosphino)éthane (dppe), conduit aux complexes correspondants
avec remplacement du PPh3, soit respectivement les [h5:s-Me2C(C5H4)(C2B10H10)]M(2,6-Me2-C6H3NC) (M = Co (9); Ni
(10)), [h5:s-Me2C(C9H6)(C2B10H10)]M[1,3-(2,6-i-Pr2C6H3NC)2(C3N2H2] (M = Co (11); Ni (12)) [h5:s-Me2C(C5H4)
(C2B10H10)]Ni(PCy3) (13) ou {[h5:s-Me2C(Me2C5H4)(C2B10H10)]Co}2(dppe) (14). Ces complexes ont été caractérisés par di-
verses techniques spectroscopiques et par des analyses élémentaires. Les structures moléculaires des composés 4–14 ont de
plus été confirmées par des diffractions de rayons-X sur des cristaux uniques.
Mots‐clés : carborane, cyclopentadiényle, complexes du cobalt, complexes du nickel, réaction de substitution.
[Traduit par la Rédaction]
[h5:s-Me2C(C5H4)(C2B10H10)]Ru(CH3CN)2 can also react
with 3 equiv of terminal alkynes ArC≡CH to form the unex-
pected tricyclic compounds with the activation of the incor-
porated C5H4 ring.4f
It has been documented that the Co and Ni complexes
show some common features with the Ru ones in [2+2+2]
cyclotrimerization of alkynes and C–C coupling reactions.5
Connected to this and to understand the similarities and dif-
ferences among late transition-metal complexes with linked
cyclopentadienyl–carboranyl ligands, we extended our re-
search to include cobalt and nickel metals. We report herein
the synthesis, structure, and reactivity of Co and Ni complexes
Introduction
Linked cyclopentadienyl/indenyl/fluorenyl–carboranyl ligands
have been widely used for the synthesis of constrained-
geometry transition-metal complexes,1–3 in which the non-
traditional metal–carbon(cage) (M–Ccage) bonds are generally
inert toward electrophiles because of steric reasons.1e,1f On
the other hand, they can offer transition-metal complexes
unique features.4 For example, the constrained-geometry
ruthenium complexes, [h5:s-Me2C(C5H4)(C2B10H10)]Ru(L2)
(L = NHR2, CH3CN) can react with alkynes to produce
Ru–carbene, –diene, and –bisvinylidene complexes bearing
the [Me2C(C5H4)(C2B10H10)]2– ligand.4 In addition,
Received 29 April 2011. Accepted 4 July 2011. Published at www.nrcresearchpress.com/cjc on 10 November 2011.
D. Liu, Z. Qiu, H.-S. Chan, and Z. Xie. Department of Chemistry and Center of Novel Functional Molecules, The Chinese University of
Hong Kong, Shatin, New Territories, Hong Kong, China.
Corresponding author: Zuowei Xie (e-mail: zxie@cuhk.edu.hk).
This article is part of a Special Issue dedicated to Professor Tak-Hang Chan.
Can. J. Chem. 90: 108–117 (2012)
doi:10.1139/V11-115
Published by NRC Research Press

Liu et al.
109
Scheme 1. Synthesis of cobalt and nickel complexes.
Fig. 1. Molecular structure of [h5:s-Me2C(C5H4)(C2B10H10)]NiPPh3
(5).
M
PPh3
H
1
M = Co (4), Ni (5)
1) 2nBuLi/THF
2) MCl2(PPh3)2
M
PPh3
H
M = Co (6), Ni (7)
2
NMe2
NMe2
Ni PPh3
H
Fig. 2. Molecular structure of [h5:s-Me2C(C9H6)(C2B10H10)]NiPPh3
(7).
3
8
bearing carbon-linked cyclopentadienyl/indenyl–carboranyl
ligands.
Results and discussion
Synthesis and structure
Treatment of Li2[Me2C(C5H4)(C2B10H10)]2d with 1 equiv
of MCl2(PPh3)2 (M = Co, Ni) in THF at room temperature
afforded, after recrystallization from Et2O, constrained-
geometry transition-metal complexes [h5:s-Me2C(C5H4)
(C2B10H10)]M(PPh3) (M = Co (4) or Ni (5)) in ~90%
isolated yields (Scheme 1). In a similar manner, com-
plexes [h5:s-Me2C(C9H6)(C2B10H10)]M(PPh3) (M = Co
(6) or Ni (7)) and [h5:s-Me2C(Me2NCH2CH2C5H3)
(C2B10H10)]Ni(PPh3) (8) were also synthesized from
the interaction of Li2[Me2C(C9H6)(C2B10H10)]2e or
Li2[Me2C(Me2NCH2CH2C5H3)(C2B10H10)] with 1 equiv of
MCl2(PPh3)2 in 63%–79% isolated yields, respectively
(Scheme 1).
distances and angles around the metal atoms are listed in
Table 1 for comparison. It is noted that the appended N
atom in 8 does not substitute the P atom to form the intra-
molecular coordination to the Ni atom as the N atom is a
harder base than the P atom.
The distances between the Co atom and the five-membered
ring atoms (Co–Cring) range from 2.028(3) to 2.126(3) Å in 4
and from 2.044(4) to 2.259(4) Å in 6. These values are compa-
rable to the 2.102(2) Å in (h5-C5H5)Co(PPh3)[h1(N)-N(O)Me],6
to the 2.06(5) Å in (h5-C5H5)Co(S2C2B10H10),7 and to the
2.154(9) Å in (h5-C9H6)(C3H7)(PMe3)2CoI.8 The average
Complexes 4 and 6 were paramagnetic species, which did
not provide useful NMR information. For complexes 5, 7,
1
and 8, the H and 13C NMR spectra showed the presence of
the ligand and coordinated PPh3 with an 1:1 molar ratio.
Their 11B NMR spectra exhibited the same 2:3:5 pattern.
The 31P NMR spectra displayed a singlet at 47.3 ppm for 5,
33.8 ppm for 7, and 36.5 ppm for 8, respectively. The com-
positions of complexes 4–8 were confirmed by elemental
analyses.
Ni–Cring distances of 2.145(6) Å in 5, 2.17
0.01 Å in 7,
and 2.131(3) Å in 8 are very close to each other. They are also
similar to the 2.102(6) Å in [Ni(h5-C5H5)(PPh3)C≡CCHO],9
to the 2.182(3) Å in [(h5-1-TMS-C9H5)NiCl(PPh3),10 to the
2.114(7) Å in (h5:h1-C5H4CH2CH2NMe2)Ni(C12H8N),11 and to
the 2.098(9) Å in [(h5-C5H4CH2CH2NMe2)Ni(dmpe)][PF6].12
The metal – cage carbon distances (M–Ccage) between 1.95
and 2.01 Å for 4–8 are comparable to the 1.998(9)–2.013(9) Å
in [Ni{(C2B10H10)2}2]2–,13 to the 2.051(12)–2.070(12) Å
The solid-state structures of 4–8 as revealed by single-
crystal X-ray analyses show that the metal atoms are h5-bound
to the cyclopentadienyl ligand (in 4, 5, and 8) or indenyl
ligand (in 6 and 7), s-bound to one cage carbon atom, and
coordinated to a triphenylphosphine in a trigonal planar ge-
ometry, leading to the formation of 17 e– cobalt and 18 e–
nickel complexes. The representative structures of 5, 7, and
8 are shown in Figs. 1–3, respectively. The selected bond
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110
Can. J. Chem. Vol. 90, 2012
Fig. 3. Molecular structure of [h5:s-Me2C(Me2NCH2CH2C5H3)
(C2B10H10)]NiPPh3 (8).
tural with a trigonal planar geometry. The representative
structure of 9 is shown in Fig. 4. The average M–Cring
bond distances of 2.074(3)/2.099(4) Å in Co (9)/Ni (10)
are comparable to those of 2.085(3)/2.145(6) Å observed in
4/5, and the M–Ccage bond distances of 1.922(3)/1.898(3) Å
in 9/10 are slightly shorter than those of 1.989(3)/1.975(5) Å
found in 4/5. The M–C bond distances of 1.838(3)/1.790(3) Å
in 9/10 compare to those of 1.87(1)/1.89(1) Å in [Co(LC=O
:
N2(SO)2)(CNt-Bu)2]–,19 to 1.772(18)/1.963(18)
CoBr(PhCOCH)(CNC6H3Me2-2,6)6,20 to 1.787(3)
Ni(triphos)(CNC6H3Me2-2,6),21 to 1.820(4)
Å
in
in
in
Å
Å
Ni{S2P(O)(OEt)}(CNC6H3Me2-2,6)(PCy3),22 and to 1.789(9)/
1.789(8) Å in [Ni(m-t-Bu2As)(p-tol-NC)2]2.23
Reaction of 4 or 5 with 1 equiv of NHC (1,3-bis(2,6-
diisopropylphenyl)-1,3-dihydro-2H-imidazol-2-ylidene)
in
toluene at room temperature afforded [h5:s-Me2C(C5H4)
(C2B10H10)]M[C(2,6-i-Pr2C6H3–NCH)2] (M = Co (11) or
Ni (12)) in 51% and 60% isolated yield, respectively
(Scheme 2). The characteristic 13C resonance at
163.1 ppm corresponding to the NHC carbene carbon was
observed in the 13C NMR spectrum of 12. Its 11B NMR
spectrum showed a 2:3:5 pattern.
The structures of complexes 11 and 12 were confirmed by
single-crystal X-ray analyses. They are isomorphous and iso-
structural. The metal atom is h5-bound to the Cp ring, s-
bound to the cage carbon atom, and coordinated to the
carbene atom in a trigonal planar geometry. The representa-
tive structure of 11 is shown in Fig. 5. The average M–Cring
/
in [Co{(C2B10H10)2}2]2–,13 and to the 1.972(5)
Å in
M–Ccage bond distances of 2.143(3)/2.152(4) Å in 11 and
2.003(3)/1.945(3) Å in 12 are comparable to the correspond-
ing values observed in 4 and 5, respectively. The Co–CNHC
bond distance of 2.011(2) Å in 11 is similar to that of
2.043(2)/2.019(2) Å in [(TIMENxyl)Co][BPh4]2 (TIMEN =
tris[2-(3-arylimidazol-2-ylidene)ethyl]amine; xyl = 2,6-dimeth-
ylphenyl))24 and to 1.914(2) Å in (h5-C5H4)Co[C(2,6-i-
Pr2C6H3–NCH)2]Me2.25 The Ni–CNHC bond distance of
1.934(2) Å in 12 is somewhat longer than the 1.882(4) Å
in Cp[(h2:h2-CH2=CHCH2NCHCHNMe)]C]Ni,26 than the
1.886(3) Å in (C9H7)[(i-PrNCH)2C]NiCl,27 than the 1.888(4) Å
in (C9H7)[(i-PrNCH)2C]NiBr,27 and than the 1.901(3) Å in
[(m-MeOC6H4CH2NCHCHNCH2CH2PPh2)C]2NiCl2.28
[h:s-(2-C5H4NCH2C2B10H10)]2Ni.14
The metal–phosphorus distances (M–P) in 4–8 fall in the
range 2.19–2.25 Å. They are comparable to the 2.184(1) Å
in (h5-C5H5)Co(PPh3)[h1(N)-N(O)Me],6 to the 2.146(1) Å in
(h5-C9H6)Co(CO)(PPh3),15 to the 2.29(1)/2.20(1)
Å
Å
in
in
(PPh3)2Ni(C2B10H10),16 to the 2.211(2)/2.214(2)
{(PPh3)2Ni[m-(h5-C5H4)CMe2(h5-C5H4)]Ni(PPh3)2}{PF6}2,17
and to the 2.134(1) Å in Cp*Ni(PPh3)(CH2COt-Bu).18
Reactivity
The substitution reactions of 4 and 5 with various Lewis
bases were examined to gain information on the lability of
the PPh3 ligand. The results showed that the PPh3 in 4 and 5
were easily replaced by isocyanide, N-heterocyclic carbene
(NHC), and other phosphines.
Interaction of 5 with 1 equiv of PCy3 (Cy = cyclohexyl) in
refluxing toluene afforded [h5:s-Me2C(C5H4)(C2B10H10)]Ni(PCy3)
(13) in 57% isolated yield. The room-temperature reaction
was very slow. An equimolar reaction of 4 with 0.5 equiv
of dppe (1,2-bis(diphenylphosphino)ethane) gave {[h5:s-
Me2C(C5H4)(C2B10H10)]Co}2(dppe) (14) in 62% isolated
yield (Scheme 2). The substitution of PPh3 in 5 by PCy3
Treatment of 4 or 5 with 1 equiv of 2,6-dimethylphenyliso-
cyanide at room temperature in toluene afforded, after recrys-
tallization from Et2O, the PPh3 displacement products,
[h5:s-Me2C(C5H4)(C2B10H10)]M(CNC6H3Me2-2,6) (M = Co
(9) or Ni (10)) in 77% and 59% isolated yield, respectively
(Scheme 2). The reactions were monitored by 31P NMR
spectra. Complex 10 showed a distinct NMR spectrum
from its parent complex 5. Except for the resonances corre-
sponding to the protons of the bridging ligand, signals in
the range 6.66–6.51 ppm assignable to the aromatic protons
and one singlet at 2.11 ppm attributable to the methyl pro-
tons on the phenyl ring were observed in the 1H NMR
spectrum. The characteristic resonance of the N=C at
162.8 ppm was observed in the 13C NMR spectrum. The
1
was confirmed by H and 31P NMR spectra. In addition to
the resonances assignable to the protons of the bridging li-
gand, multiplets in the region 2.11–1.07 ppm corresponding
to the cyclohexyl protons were observed in the 1H NMR
spectrum. Its 31P NMR spectrum showed a singlet at
44.4 ppm compared with the 47.3 ppm in 5.
The molecular structure of 13 is shown in Fig. 6. The Ni
atom is h5-bound to the cyclopentadienyl ring, s-bound to
one cage carbon atom, and coordinated to the P atom of the
tricyclohexylphosphine in a trigonal planar geometry. The
average Ni–Cring/Ni–Ccage/Ni–P bond distances of 2.140(5)/
1.949(5)/2.226(1) Å are very close to those of 2.145(6)/
1.975(5)/2.210(1) Å in 5. On the other hand, as revealed by
11B NMR spectrum showed a 1:2:3:4 pattern.
The structures of both 9 and 10 were confirmed by single-
crystal X-ray analyses. They are isomorphous and isostruc-
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Liu et al.
111
Table 1. Selected bond lengths (Å) and angles (°) in compounds 4–14.
Bond length (Å)
Bond angle (°)
M–Centa
1.706
1.765
1.763
1.800
1.752
1.689
1.722
1.762
1.786
1.770
1.697
M–X
Cent–M–Ccage
Cring–Cbridge–Ccage
113.9(2)
114.1(4)
114.7(3)
114.3(2)
114.4(2)
114.1(2)
114.0(2)
114.3(2)
114.2(2)
114.1(4)
114.3(2)
a
Compd.
4
5
6
7
8
9
10
11
12
13
14
M–Ccage
1.989(3)
1.975(5)
2.008(5)
1.950(3)
1.960(2)
1.922(3)
1.898(3)
2.003(3)
1.945(3)
1.949(5)
1.951(3)
Av. M–Cring
2.085(3)
2.145(6)
2.15 0.01
2.17 0.01
2.131(3)
2.074(3)
2.099(4)
2.143(3)
2.152(4)
2.140(5)
2.084(4)
2.209(1) (X = P)
2.210(1) (X = P)
2.247(1) (X = P)
2.194(1) (X = P)
2.188(1) (X = P)
1.838(3) (X = C)
1.790(3) (X = C)
2.011(2) (X = C)
1.934(2) (X = C)
2.226(1) (X = P)
2.216(1) (X = P)
122.6
122.0
123.3
122.4
122.0
124.0
123.4
121.0
120.5
121.4
123.4
aCent: the centroid of the five-membered ring.
Scheme 2. Reactivity of cobalt and nickel complexes.
NC
M
C
N
9
M = Co ( ), Ni (
10
)
N
N
iPr
M
iPr
N
N
iPr
iPr
M
PPh3
M = Co (11), Ni (12)
M = Co (4), Ni (5)
PCy3
Ni PCy3
13
Ph
Ph
dppe
Co
Ph
Co
P
P
Ph
14
single-crystal X-ray analyses, 14 is a dinuclear complex
(shown in Fig. 7), in which two trigonal planar
[h5:s-Me2C(C5H4)(C2B10H10)]Co moieties are connected by
a Ph2PCH2CH2PPh2 linkage resulting in the formation of a
17 e– complex for each Co atom. The average Co–Cring/Co–
bases. However, they are inert toward alkynes, nitriles, and
H2. Complexes 9 and 10 are also very thermally stable. The
inertness of the M–Ccage s bonds in these late transition-
metal complexes can be ascribed to the steric hindrance of
the icosahedral carborane cage.1e,1f
C
cage/Co–P bond distances of 2.084(4)/1.951(3)/2.216(1) Å are
Conclusion
A series of cobalt and nickel complexes bearing carbon-
bridged cyclopentadienyl/indenyl/C5H3CH2CH2NMe2–carboranyl
very similar to the 2.085(3)/1.989(3)/2.207(1) Å observed in 4.
The aforementioned results show that the coordinated PPh3
in complexes 4 and 5 is labile and can be replaced by Lewis
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112
Can. J. Chem. Vol. 90, 2012
Fig. 4. Molecular structure of [h5:s-Me2C(C5H4)(C2B10H10)]Co
(CNC6H3Me2-2,6) (9).
Fig. 6. Molecular structure of [h5:s-Me2C(C5H4)(C2B10H10)]NiPCy3
(13).
Fig. 5. Molecular structure of [h5:s-Me2C(C5H4)(C2B10H10)]Co[1,3-
(2,6-i-Pr2C6H3)2C3N2H2] (11).
Fig. 7. Molecular structure of {[h5:s-Me2C(C5H4)(C2B10H10)]Co}2
(dppe) (14).
NiCl2(PPh3)2,31 and CoCl2(PPh3)2 were prepared accord-
32
ing to literature methods. Infrared spectra were obtained
from KBr pellets prepared in the glovebox on a PerkinElmer
1600 Fourier transform spectrometer. 1H and 13C NMR
spectra were recorded on a Bruker DPX 300 spectrometer
at 300 and 75.5 MHz, respectively. 11B and 31P NMR
spectra were recorded on a Varian Inova 400 spectrometer
at 128 and 162 MHz, respectively. All chemical shifts
were reported in d units with references to the residual
protons of the deuterated solvents for proton and carbon
chemical shifts, to external BF3·OEt2 (0.00 ppm) for
boron chemical shifts, and to external 85% H3PO4
(0.00 ppm) for phosphorus chemical shifts. Elemental
analyses were performed by the Shanghai Institute of Or-
ganic Chemistry, Chinese Academy of Sciences, China.
ligands were synthesized via salt metathesis reactions be-
tween the dilithium salts of these ligands and metal halides.
They adopt a trigonal planar geometry, leading to a 17 e–
cobalt and a 18 e– nickel complex, respectively. The phos-
phines in [h5:s-Me2C(C5H4)(C2B10H10)]M(PPh3) are labile
and can be displaced by other Lewis bases. However, the
M–Ccage bonds in these complexes are inert toward electro-
philes such as alkynes, nitriles, isonitriles, and H2 because
of the steric hindrance of the carboranyl ligand.
Experimental section
General procedures
All experiments were performed under an atmosphere of
dry dinitrogen with the rigid exclusion of air and moisture
using standard Schlenk or cannula techniques or in a glove-
box. All organic solvents were refluxed over sodium benzo-
phenone ketyl for several days and freshly distilled prior to
use. All chemicals were purchased from either Sigma-Aldrich
or Acros Chemical Co. and used as received unless otherwise
Preparation of Me2C(Me2NCH2CH2C5H4)(C2B10H11) (3)
To a toluene/Et2O (2:1) solution (15 mL) of o-C2B10H12
(1.44 g, 10.0 mmol) was added a 1.60 mol/L solution of
n-BuLi in hexane (12.6 mL, 20.2 mmol) at 0 °C, and the
reaction mixture was warmed to room temperature and
stirred for 2 h. The resulting Li2C2B10H10 solution was
then cooled to 0 °C, to which was slowly added a solution
noted.
Me2C(C5H5)(C2B10H11),2d
Me2NCH2CH2Cl,29
Me2NCH2CH2C5H3CMe2,30
Me2C(C9H7)(C2B10H11),2e
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Liu et al.
113
of dimethyl(dimethylaminoethyl)fulvene (2.12 g, 12.0 mmol)
in a toluene/Et2O (2:1) mixture (9 mL). The reaction mix-
ture was maintained at 0 °C for 1 h, slowly warmed to
room temperature, and then refluxed overnight. After re-
moval of the solvent, Et2O was added. The solution was
quenched with a saturated NH4Cl solution. The organic
layer was separated and washed with water and then dried
with anhydrous MgSO4. After removal of the solvent by ro-
tary evaporation, the residue was subjected to column chro-
matography on silica gel to give 3 as a yellow oil (2.66 g,
dure as reported for 4; yield: 0.49 g (79%). IR (KBr, cm–1)
nBH: 2593 (vs). Anal. calcd for C32H37B10CoP (6): C 62.03,
H 6.02; found: C 62.30, H 6.17.
Preparation of [h5:s-Me2C(C9H6)(C2B10H10)]Ni(PPh3) (7)
This complex was prepared as green crystals from
Me2C(C9H7)(C2B10H11) (0.30 g, 1.0 mmol), n-BuLi
(1.60 mol/L, 1.25 mL, 2.0 mmol), and NiCl2(PPh3)2
(0.65 g, 1.0 mmol) in THF (20 mL) using the same proce-
dure as reported for 4; yield: 0.43 g (69%). IR (KBr, cm–1)
1
83%). IR (KBr, cm–1) nBH: 2521 (vs). H NMR (CDCl3) d:
1
nBH: 2581 (vs). H NMR (C6D6) d: 7.75 (d, J = 8.0 Hz,
6.25–5.70 (m, 3H) (vinylic H), 3.32 + 3.15 (s, 1H) (cage
CH), 2.97 + 2.93 (s, 1H) (methylene H on Cp), 2.53 (m,
2H) (CH2CH2N(CH3)2), 2.43 (m, 2H) (CH2CH2N(CH3)2),
2.28 + 2.25 (s, 6H) (CH2CH2N(CH3)2), 1.58 + 1.50 (s, 6H)
(C(CH3)2). 13C{1H} NMR (CDCl3) d: 150.1, 149.2, 133.2,
130.9, 127.1, 126.9, 126.3, 126.1 (vinylic C), 84.8 (cage
C), 63.9, 63.4 (N(CH3)2), 59.5, 58.8 (CH2CH2N(CH3)2),
45.5, 42.9 (CH2CH2N(CH3)2), 44.3, 42.1 (methylene C on
Cp), 42.1, 40.4 (C(CH3)2), 31.5, 30.8, 29.0, 28.3 (C(CH3)2).
1H), 6.78 (t, J = 8.0 Hz, 2H), 6.45 (d, J = 3.6 Hz, 1H),
5.13 (d, J = 8.0 Hz, 1H), 3.88 (t, J = 3.6 Hz, 1H) (C9H6),
7.32 (m, 6H), 6.99 (m, 9H) (C6H5), 1.60 (s, 3H), 1.54 (s,
3H) ((CH3)2C). 13C{1H} NMR (C6D6) d: 135.0, 135.8,
134.4, 132.8, 132.7, 131.9, 130.9, 129.6, 126.6, 125.3,
123.8, 121.9, 117.3, 106.5 (C9H6 + C6H5), 64.5 (cage C),
44.1 ((CH3)2C), 32.3, 31.3 ((CH3)2C). 11B{1H} NMR
(C6D6) d: –3.2 (2B), –6.4 (3B), –9.3 (5B). 31P{1H} NMR
(C6D6) d: 33.8. Anal. calcd for C32H37B10NiP (7): C 62.05,
H 6.02; found: C 62.07, H 5.80.
11B{1H} NMR (CDCl3): d –3.9 (2B), –8.9 (2B), –11.3
1
(2B), –13.5 (4B). The H and 13C NMR data suggested that
Preparation of [h5:s-Me2C(C5H3CH2CH2NMe2)
(C2B10H10)]Ni(PPh3) (8)
This complex was prepared as green crystals from
Me2C(C5H4CH2CH2NMe2)(C2B10H11) (0.32 g, 1.0 mmol),
n-BuLi (1.60 mol/L, 1.25 mL, 2.0 mmol), and NiCl2(PPh3)
3 was a mixture of isomers with the Me2NCH2CH2 group
bound to either the sp2 or sp3 carbon of the Cp ring.2d
Preparation of [h5:s-Me2C(C5H4)(C2B10H10)]Co(PPh3) (4)
An n-BuLi solution in n-hexane (1.60 mol/L, 1.25 mL,
2.0 mmol) was slowly added to a THF (10 mL) solution of
Me2C(C5H5)(C2B10H11) (0.25 g, 1.0 mmol) at –78 °C and
the mixture was warmed up to room temperature and then
stirred for 3 h. The resulting solution was slowly added to a
THF suspension (10 mL) of CoCl2(PPh3)2 (0.65 g, 1.0 mmol)
at room temperature, and the reaction mixture was stirred
overnight. After removal of the solvent, the residue was ex-
tracted with Et2O (2 × 25 mL). The Et2O solution was con-
centrated to ~10 mL. Complex 4 was isolated as brown
crystals after this solution stood at room temperature for
2 days (0.50 g, 87%). IR (KBr, cm–1) nBH: 2579 (vs). Anal.
calcd for C28H35B10CoP (4): C 59.04, H 6.19; found: C
59.08, H 6.61.
(0.65 g, 1.0 mmol) in THF (20 mL) using the same pro-
2
cedure as reported for 4; yield: 0.40 g (63%). IR (KBr, cm–1)
1
nBH: 2587 (vs). H NMR (C6D6) d: 7.69 (m, 6H), 7.02 (m,
9H) (C6H5), 6.07 (d, J = 1.5 Hz, 1H), 5.87 (s, 1H), 3.76
(d, J = 2.4 Hz, 1H) (C5H3), 2.11 (m, 2H) (CH2CH2NMe2),
1.90 (m, 2H) (CH2CH2NMe2), 1.86 (s, 6H) (N(CH3)2), 1.45
(s, 3H), 1.40 (s, 3H) ((CH3)2C). 13C{1H} NMR (C6D6) d:
135.5, 135.4, 134.8, 132.5, 132.1, 131.1, 109.8, 99.4, 97.7
(C6H5 + C5H3), 88.0 (cage C), 66.5 (CH2CH2NMe2), 45.9
(N(CH3)2), 41.5 (CH2CH2NMe2), 32.5 (C(CH3)2), 31.3, 30.7
(C(CH3)2). 11B{1H} NMR (C6D6) d: –3.6 (2B), –6.8 (3B), –9.5
(5B). 31P{1H} NMR (C6D6) d: 36.5. Anal. calcd for
C32H44B10NNiP (8): C 60.01, H 6.92, N 2.19; found: C
60.35, H 6.83, N 2.06.
Preparation of [h5:s-Me2C(C5H4)(C2B10H10)]Ni(PPh3) (5)
This complex was prepared as green crystals from
Me2C(C5H5)(C2B10H11) (0.25 g, 1.0 mmol), n-BuLi
(1.60 mol/L, 1.25 mL, 2.0 mmol), and NiCl2(PPh3)2
(0.65 g, 1.0 mmol) in THF (20 mL) using the same proce-
dure as reported for 4; yield: 0.53 g (93%). IR (KBr, cm–1)
Preparation of [h5:s-Me2C(C5H4)(C2B10H10)]Co(2,6-
Me2C6H3NC) (9)
To a toluene (5 mL) solution of [h5:s-Me2C(C5H4)
(C2B10H10)]Co(PPh3) (4; 0.29 g, 0.50 mmol) was added 2,6-
Me2C6H3NC (0.07 g, 0.50 mmol) at room temperature. The
reaction mixture was stirred at room temperature overnight.
After removal of the solvent, the residue was extracted with
Et2O (10 mL × 2). The combined Et2O solutions were con-
centrated to ~5 mL. Complex 9 was isolated as brown crys-
tals after this solution stood at room temperature for 1 day
(0.17 g, 77%). IR (KBr, cm–1) nBH: 2575 (vs). Anal. calcd
for C19H29B10CoN (9): C 52.05, H 6.67, N 3.19; found: C
52.26, H 6.70, N 3.42.
1
nBH: 2581 (vs). H NMR (C6D6) d: 7.62 (m, 6H), 7.01 (m,
9H) (C6H5), 5.96 (br, 2H), 3.70 (br, 2H) (C5H4), 1.39 (s,
6H) ((CH3)2C). 13C{1H} NMR (C6D6) d: 134.8, 134.7,
131.0, 128.9 (C6H5), 99.6, 88.2 (C5H4), 66.3 (cage C),
41.3 ((CH3)2C), 32.3 ((CH3)2C). 11B{1H} NMR (C6D6)
d: –3.5 (2B), –7.0 (3B), –9.8 (5B). 31P{1H} NMR (C6D6)
d: 47.3. Anal. calcd for C28H35B10NiP (5): C 59.07, H
6.20; found: C 58.51, H 6.25.
Preparation of [h5:s-Me2C(C9H6)(C2B10H10)]Co(PPh3) (6)
This complex was prepared as brown crystals from
Me2C(C9H7)(C2B10H11) (0.30 g, 1.0 mmol), n-BuLi
(1.60 mol/L, 1.25 mL, 2.0 mmol), and CoCl2(PPh3)2
(0.65 g, 1.0 mmol) in THF (20 mL) using the same proce-
Preparation of [h5:s-Me2C(C5H4)(C2B10H10)]Ni(2,6-
Me2C6H3NC) (10)
This complex was prepared as green crystals from
[h5:s-Me2C(C5H4)(C2B10H10)]Ni(PPh3) (5; 0.29 g, 0.50 mmol)
and 2,6-Me2C6H3NC (0.07 g, 0.50 mmol) in toluene (5 mL)
Published by NRC Research Press

Table 2. Crystal data and summary of data collection and refinement details for compounds 4–9.
Compound
Parameter
Empirical formula
Formula weight
Crystal size (mm)
Crystal system
Space group
a (Å)
b (Å)
c (Å)
a (°)
b (°)
4
5
6
7
8
9
C28H35B10CoP
569.6
0.50×0.40×0.10
Monoclinic
P21/c
11.562(2)
20.123(4)
13.887(3)
90
114.60(3)
90
C28H35B10NiP
569.3
0.50×0.30×0.20
Monoclinic
P21/n
11.720(2)
20.529(4)
13.938(3)
90
114.86(3)
90
C32H37B10CoP
619.6
0.50×0.40×0.10
Monoclinic
P21/c
12.490(3)
13.598(3)
19.877(4)
90
90.00(3)
90
C32H37B10NiP
619.4
0.50×0.40×0.40
Monoclinic
P21/c
12.322(2)
13.403(2)
19.755(3)
90
91.25(1)
90
C32H44B10NNiP
640.5
0.40×0.30×0.20
Triclinic
P(–1)
10.510(2)
13.019(3)
13.996(3)
101.90(3)
106.00(3)
98.73(3)
1756.4(6)
2
C19H29B10CoN
438.5
0.40×0.30×0.30
Orthorhombic
P212121
12.585(5)
12.826(5)
14.284(6)
90
90
90
g (°)
V (Å3)
2937.8(10)
4
1.288
3042.7(10)
4
1.243
3375.9(12)
4
1.219
3261.8(7)
4
1.261
2305.6(16)
4
1.263
Z
Dc (Mg m–3)
1.211
0.622
m (mm–1)
0.658
0.709
0.578
0.667
0.752
Radiation (l, Å)
F(000)
Mo K (0.71073)
1180
Mo K (0.71073)
1184
Mo K (0.71073)
1284
Mo K (0.71073)
1288
Mo K (0.71073)
672
Mo K (0.71073)
908
q range (°)
Observed reflections
Parameters
R indices (I > 2s(I))a
1.9–25.6
1.9–25.4
1.6–25.0
1.6–25.0
1.5–25.5
2.0–28.0
4864
4651
5388
5744
5630
5763
361
361
397
397
406
280
R1 = 0.046
wR2 = 0.119
1.158
R1 = 0.075
wR2 = 0.189
1.148
R1 = 0.094
wR2 = 0.242
1.142
R1 = 0.036
wR2 = 0.085
1.076
R1 = 0.038
wR2 = 0.105
1.086
R1 = 0.041
wR2 = 0.086
1.020
Goodness-of-fit (S)b
aR1 = ∑||F0| – |Fc||/∑|F0|; wR2 = {∑[w(F0 – Fc2)2]/∑[w(F0 )2]}1/2
.
2
2
bS = {∑[w(F0 – Fc2)2]/ (n – p)}1/2 (n = No. of data; p = No. of parameters varied).
2

Liu et al.
115
Table 3. Crystal data and summary of data collection and refinement details for compounds 10–14.
Compound
Parameter
Empirical formula
Formula weight
Crystal size (mm)
Crystal system
Space group
a (Å)
b (Å)
c (Å)
a (°)
b (°)
10
11
12
13
14
C19H29B10NNi
438.2
C37H56B10CoN2
695.9
0.50×0.40×0.40
Monoclinic
P21/n
10.585(2)
20.471(4)
19.337(4)
90
98.77(3)
90
C37H56B10N2Ni
695.7
0.50×0.40×0.30
Monoclinic
P21/n
10.447(2)
20.103(4)
19.072(4)
90
90.86(3)
90
C30H58B10NiO0.5
624.5
0.30×0.20×0.10
Triclinic
P(–1)
10.233(2)
11.973(2)
15.377(2)
98.02(1)
95.42(1)
110.62(1)
1724.8(5)
2
P
C54H84B20Co2O2P2
1161.2
0.40×0.30×0.20
Monoclinic
P21/c
10.932(1)
16.750(2)
17.431(2)
90
103.11(1)
90
0.50×0.40×0.30
Orthorhombic
P212121
12.462(3)
12.866(3)
14.204(3)
90
90
90
2277.4(8)
4
1.278
g (°)
V (Å3)
4141.1(14)
4
1.116
3957.5(14)
4
1.168
3108.4(5)
2
1.241
Z
Dc (Mg m–3)
1.203
0.631
m (mm–1)
0.859
0.442
0.519
0.625
Radiation (l, Å)
F(000)
Mo K (0.71073)
912
Mo K (0.71073)
1476
Mo K (0.71073)
1480
Mo K (0.71073)
670
Mo K (0.71073)
1216
q range (°)
Observed reflections
Parameters
R indices (I > 2s(I))a
4.0–51.2
3.0–50.6
3.0–50.0
2.7–50.0
3.4–56.0
4056
6512
5968
6038
7716
280
451
451
394
361
R1 = 0.040
wR2 = 0.110
1.091
R1 = 0.052
wR2 = 0.134
1.131
R1 = 0.048
wR2 = 0.124
1.119
R1 = 0.055
wR2 = 0.129
1.014
R1 = 0.054
wR2 = 0.129
1.034
Goodness-of-fit (S)b
aR1 = ∑||F0| – |Fc||/∑|F0|; wR2 = {∑[w(F0 – Fc2)2]/∑[w(F0 )2]}1/2
.
2
2
bS = {∑[w(F0 – Fc2)2]/ (n – p)}1/2 (n = No. of data; p = No. of parameters varied).
2
using the same procedure as reported for 9; yield: 0.13 g
and 1,3-(2,6-i-Pr2C6H3)2C3N2H2 (0.20 g, 0.50 mmol) in
toluene (5 mL) using the same procedure as reported for 11;
yield: 0.21 g (60%). IR (KBr, cm–1) nBH: 2573 (vs). 1H
NMR (C6D6) d: 7.25 (m, 4H), 7.12 (m, 2H) (C6H3), 6.47
(s, 2H) (C3N2H2), 5.77 (t, J = 2.4 Hz, 2H), 4.98 (d, J =
2.4Hz,2H)(C5H4),3.66(m,2H),3.09(m,2H)((CH3)2CH),1.62
(d, J = 6.6 Hz, 6H), 1.27 (d, J = 6.6 Hz, 6H), 1.01 (d, J =
6.6 Hz, 6H), 0.80 (d, J = 6.6 Hz, 6H) ((CH3)2CH), 1.24
(s, 6H) ((CH3)2C). 13C{1H} NMR (C6D6) d: 163.1 (carbene
C of NHC), 146.7, 144.8, 138.9, 130.8, 126.8, 125.5,
124.5, 120.6 (C6H3 + vinylic C of NHC), 98.6, 89.2
(C5H4), 40.5 ((CH3)2C), 30.7 ((CH3)2C), 29.4, 29.0 ((CH3)2CH),
26.1, 25.7, 23.5, 22.6 ((CH3)2CH). 11B{1H} NMR (C6D6)
d: –3.2 (2B), –6.3 (3B), –9.2 (5B). Anal. calcd for
C37H56B10N2Ni (12): C 63.88, H 8.11, N 4.03; found: C
63.86, H 8.19, N 4.25.
1
(59%). IR (KBr, cm–1) nBH: 2573 (vs). H NMR (C6D6) d:
6.66 (t, J = 7.8 Hz, 1H), 6.51 (d, J = 7.8 Hz, 2H) (C6H3),
5.65 (t, J = 2.4 Hz, 2H), 4.47 (d, J = 2.4 Hz, 2H) (C5H4),
2.11 (s, 6H) ((CH3)2C6H3), 1.29 (s, 6H) ((CH3)2C). 13C{1H}
NMR (C6D6) d: 162.7 (N=C), 132.8, 132.7, 132.0, 129.2
(C6H3), 98.5, 88.4 (C5H4), 32.3 ((CH3)2C), 30.6 ((CH3)2C6H3),
23.4 ((CH3)2C). 11B{1H} NMR (C6D6) d: –2.03 (1B), –4.11
(2B), –6.79 (3B), –8.70 (4B). Anal. calcd for C19H29B10NNi
(10): C 52.07, H 6.67, N 3.20; found: C 52.52, H 6.86, N
3.28.
Preparation of [h5:s-Me2C(C5H4)(C2B10H10)]Co[1,3-(2,6-i-
Pr2C6H3)2C3N2H2] (11)
To a toluene (5 mL) solution of [h5:s-Me2C(C5H4)
(C2B10H10)]Co(PPh3) (4; 0.29 g, 0.50 mmol) was added 1,3-
(2,6-i-Pr2C6H3)2C3N2H2 (0.20 g, 0.50 mmol) at room temper-
ature, and the reaction mixture was stirred overnight. After
removal of the solvent, the residue was extracted with Et2O
(10 mL × 2). The combined Et2O solutions were concen-
trated to ~5 mL. Complex 11 was isolated as brown crystals
after this solution stood at room temperature for 1 day
(0.18 g, 51%). IR (KBr, cm–1) nBH: 2570 (vs). Anal. calcd
for C37H56B10CoN2 (11): C 63.86, H 8.11, N 4.03; found: C
63.35, H 7.67, N 4.01.
Preparation of [h5:s-Me2C(C5H4)(C2B10H10)]Ni(PCy3) (13)
To a toluene (5 mL) solution of [h5:s-Me2C(C5H4)
(C2B10H10)]Ni(PPh3) (5; 0.29 g, 0.50 mmol) was added
PCy3 (0.14 g, 0.50 mmol) at room temperature. The reaction
mixture was refluxed for 1 day. After removal of the solvent,
the residue was extracted with Et2O (10 mL × 2). The com-
bined Et2O solutions were concentrated to ~5 mL. Complex
13 was isolated as green crystals after this solution stood at room
temperature for 1 day (0.18 g, 57%). IR (KBr, cm–1) nBH: 2573
(vs). 1H NMR (C6D6) d: 5.94 (m, 2H), 4.23 (m, 2H)
(C5H4), 2.11–1.07 (m, 33H) (Cy), 1.39 (s, 6H) ((CH3)2C).
Preparation of [h5:s-Me2C(C5H4)(C2B10H10)]Ni[1,3-(2,6-i-
Pr2C6H3)2C3N2H2] (12)
13C{1H} NMR (C6D6) d: 99.7, 90.2 (C5H4), 66.3 (cage C),
32.3, 31.2, 29.7, 28.1, 27.1, 23.4, 15.9 ((CH3)2C + P(C6H11)3).
This complex was prepared as green crystals from
[h5:s-Me2C(C5H4)(C2B10H10)]Ni(PPh3) (5; 0.29 g, 0.50 mmol)
Published by NRC Research Press

116
Can. J. Chem. Vol. 90, 2012
11B{1H}NMR(C6D6)d:–2.4(5B),–6.0(2B),–8.9(3B).31P{1H}
NMR (C6D6) d: 44.4. Anal. calcd for C30H58B10NiO0.5P (13 +
0.5Et2O): C 57.69, H 9.36; found: C 58.09, H 9.11.
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Preparation of {[h5:s-Me2C(C5H4)(C2B10H10)]Co}2(dppe)
(14)
This complex was prepared as brown crystals from
[h5:s-Me2C(C5H4)(C2B10H10)]Co(PPh3) (4; 0.29 g, 0.50 mmol)
and dppe (0.10 g, 0.25 mmol) in toluene (5 mL) using the
same procedure as reported for 13; yield: 0.19 g (62%). IR
(KBr, cm–1) nBH: 2573 (vs). Anal. calcd for C46H64B20Co2P2
(14 + 2Et2O): C 54.54, H 6.37; found: C 54.24, H 6.25.
X-ray structure determination
All single crystals were immersed in Paraton-N oil and
sealed under N2 in thin-walled glass capillaries. Data were
collected at 293 K on a Bruker SMART 1000 CCD diffrac-
tometer using Mo Ka radiation. An empirical absorption cor-
rection was applied using the SADABS program.33 All
structures were solved by direct methods and subsequent
Fourier difference techniques and refined anisotropically for
all non-hydrogen atoms by full-matrix least-squares calcula-
tions on F2 using the SHELXTL program package.34 All hy-
drogen atoms were geometrically fixed using the riding
model. Molecular structures of 13 and 14 showed the solva-
tion of half and two Et2O molecules, respectively. For the
noncentrosymmetric structures 9 and 10, the appropriate
enantiomorph of 9 was chosen by refining Flack’s parameter
c toward zero;35 however, the appropriate enantiomorph of
10 was unable to be chosen as its c ≈ 0.5 after refinement.
Crystal data and details of data collection and structure re-
finements were given in Tables 2 and 3 (X-ray data can be
found in the Supplementary data).
Supplementary data
Supplementary data are available for this article through
the journal Web site at http://nrcresearchpress.com/doi/
suppl/10.1139/v11-115. CCDC 823250–823260 contain the
X-ray data in CIF format for this manuscript (compounds
4–14). These data can be obtained, free of charge, via
http://www.ccdc.cam.ac.uk/cgi-bin/catreq.cgi (Or from the
Cambridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1Ez, UK; fax +44 1223 336033; or e-mail
deposit@ccdc.cam.ac.uk).
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Acknowledgment
The work described in this article was supported by grants
from the Research Grants Council of the Hong Kong Special
Administration Region (Project No. 404609) and Direct
Grant (Project No. 2060407).
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