Reactions of [η5:σ-Me2C(C5H4)(C 2B10H10)]Ru(COD) with Lewis bases: Synthesis, structure, and electrochemistry of ruthenium amine, nitrile, carbene, phosphite and phosphine comple

Article abstract of DOI:10.1016/j.jorganchem.2006.03.022

Treatment of [η⁵:σ-Me₂C(C₅H₄) (C₂B₁₀H₁₀)]Ru(COD) (1) with phosphites, phosphines, amines or N-heterocyclic carbene in THF afforded the COD displacement complexes [η⁵:σ

Full text of DOI:10.1016/j.jorganchem.2006.03.022

Journal of Organometallic Chemistry 691 (2006) 3071–3082
www.elsevier.com/locate/jorganchem
Reactions of [g5:r-Me2C(C5H4)(C2B10H10)]Ru(COD) with Lewis
bases: Synthesis, structure, and electrochemistry of ruthenium
amine, nitrile, carbene, phosphite and phosphine complexes
a
a
b
a,
*
Yi Sun , Hoi-Shan Chan , Pierre H. Dixneuf , Zuowei Xie
a
Department of Chemistry, The Chinese University of Hong Kong, Shatin, New Territories, Hong Kong, China
Institut de Chimie de Rennes, UMR 6509 CNRS-Universite´ de Rennes, Organome´talliques et Catalyse, Campus de Beaulieu, 35042 Rennes, France
b
Received 8 February 2006; accepted 14 March 2006
Available online 18 March 2006
Abstract
Treatment of [g5:r-Me2C(C5H4)(C2B10H10)]Ru(COD) (1) with phosphites, phosphines, amines or N-heterocyclic carbene in THF affor-
ded the COD displacement complexes [g5:r-Me2C(C5H4)(C2B10H10)]Ru[P(OEt)3]2 (2), [g5:r-Me2C(C5H4)(C2B10H10)]Ru[PPh2(OEt)]2 (3),
[g5:r-Me2C(C5H4)(C2B10H10)]Ru[NH2CH2CH2Pri]2 (4), [g5:r-Me2C(C5H4)(C2B10H10)]Ru(NH2Prn)2 (5), [g5:r-Me2C(C5H4)(C2B10H10)]-
Ru (g2-NH2CH2CH2NH2) (6), [g5:r-Me2C(C5H4)(C2B10H10)]Ru[g2-NH(CH3)CH2CH2NH(CH3)] (7) or [g5:r-Me2C(C5H4)(C2B10H10)]-
Ru[NHC]2 (8, NHC = 1,3,4,5-tetramethylimidazol-2-yilidene), respectively. Ruthenium–amine complexes were much more labile than 1.
Upon exposure to moisture, 5 was converted into [{g5:r-Me2C(C5H4)(C2B10H10)}Ru(l-H2O)]2 (9). Reactions of 5 with PR3 (R = PPh3,
Cy), TMEDA (TMEDA = N,N,N0,N0-tetramethylethylenediamine) and CH3CN afforded the corresponding amine replacement products
[g5:r-Me2C(C5H4)(C2B10H10)]Ru(NH2Prn)(PPh3) (10), [g5:r-Me2C(C5H4)(C2B10H10)]Ru(NH2Prn)(PCy3) (11), [g5:r-Me2C(C5H4)-
(C2B10H10)]Ru(TMEDA) (12) and [g5:r-Me2C(C5H4)(C2B10H10)]Ru(NCCH3)2 (13). These results indicated that the steric factor domi-
nated these substitution reactions. The electrochemical studies showed that the electron richness of the Ru atom decreased in the order
L2Ru(NHC)2 > L2Ru(amine)2 > L2Ru(NCMe)2 > L2Ru(P)2. All of these complexes were fully characterized by various spectroscopic tech-
niques and elemental analyses. The molecular structures of 2, 3, 5–10, 12 and 13 were further confirmed by single-crystal X-ray analyses.
ꢀ 2006 Elsevier B.V. All rights reserved.
Keywords: Carborane; Cyclopentadienyl; Electrochemistry; Ruthenium complexes; Steric effect; Substitution reactions
1. Introduction
addition of carbene to alkynes and to enynes to generate
dienes and bicyclo[3.1.0]hexane derivatives [5]. The first step
of these catalytic reactions involved the leaving of the COD
ligand to form coordinatively unsaturated species.
Ruthenium half-sandwich complexes of the type (g5-
C5R5)RuXL2 [R = H, Me; X = Cl, Br; L2 = phosphines,
COD (1,5-cyclooctadiene)] are effective catalysts for C–C
bond-forming reactions [1]. For example, (g5-C5H5)RuCl-
(COD) catalyzed a variety of coupling reactions of C„C
and C@C bonds for the production of functional dienes
[2]. (g5-C5Me5)RuCl(COD) allowed the head-to-head cou-
pling of alkynes to form dienes and cyclobutenes [3] or the
sequential coupling of alkynes generating aromatic com-
pounds [4]. (g5-C5Me5)RuCl(COD) also promoted double
We recently reported constrained-geometry ruthenium
COD complexes incorporating carbon-linked carboranyl–
cyclopentadienyl (–indenyl or –fluorenyl) ligands [6]. Reac-
tivity study on [g5:r-Me2C(C5H4)(C2B10H10)]Ru(COD) (1)
showed that the COD in 1 was unable to be replaced by PR3
(R = Ph, Cy), CH3CN, pyridine or TMEDA (TMEDA =
N,N,N0,N0-tetramethylethylenediamine) even in refluxing
THF solutions, but it was able to be displaced by bidentate
tertiary phosphines and bipyridine. These results led to an
assumption that bidentate ligands with p-accepting ability
were necessary to substitute the COD in 1 [6].
*
Corresponding author. Tel.: +852 26096269; fax: +852 26035057.
E-mail address: zxie@cuhk.edu.hk (Z. Xie).
0022-328X/$ - see front matter ꢀ 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2006.03.022

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Y. Sun et al. / Journal of Organometallic Chemistry 691 (2006) 3071–3082
In the course of reactivity studies, we isolated unexpect-
to fully displace the COD in 1. On the other hand, com-
plexes 2, 3 and 6–8 did not show any reactivity toward
COD even in refluxing C6D6.
edly an amine coordinated ruthenium complex [g5:r-
Me2C(C5H4)(C2B10H10)]Ru(NH2Prn)2 from an attempted
reaction of PhC„CH with nPrNH2 using 1 as the potential
catalyst. This result indicated that the COD in 1 was able
to be replaced by simple nPrNH2, and the resultant primary
amine–ruthenium complex was stable, which encouraged
us to further investigate the displacement reactions of
COD in 1 with mono- and bi-dentate Lewis bases. We
report herein the synthesis, structure, and electrochemistry
of a series of [g5:r-Me2C(C5H4)(C2B10H10)]Ru(L2) com-
plexes (L2 = amines, diamines, nitrile, carbene, phosphites
and phosphines) derived from 1.
1
The H NMR spectra of 2–7 showed two multiplets for
Cp protons, one singlet of the Me2C protons and one set
of Lewis base protons, suggesting the pseudo-Cs symmetry
of these complexes in solution. For 8, the sterically demand-
ing NHC ligands broke the symmetry, leading to the obser-
vation of four resonances for Cp protons, two singlets of the
Me2C group and two sets of NHC protons in the 1H NMR
1
spectrum. The 13C NMR spectra were in line with the H
NMR data. Different splitting patterns were observed in
the 11B NMR spectra depending upon the nature of Lewis
bases. The solid-state IR spectra displayed a characteristic
terminal B–H absorption at ꢀ2550 cmꢁ1 for all complexes.
2. Results and discussion
2.1. COD displacement reactions
2.2. Amine displacement reactions
The COD ligand in 1 was unable to be replaced by PPh3 or
PCy3 molecules [6]. It, however, was readily substituted by
phosphites/phosphines with small cone angles. Treatment
of 1 with 2 equiv. of P(OEt)3 or PPh2(OEt) in refluxing
THF afforded the COD displacement complexes [g5:r-
Me2C(C5H4)(C2B10H10)]Ru[P(OEt)3]2 (2) or [g5:r-Me2C-
(C5H4)(C2B10H10)]Ru[PPh2(OEt)]2 (3) in 81–85% isolated
yields (Scheme 1). Upon coordination, the 31P NMR chem-
ical shifts of phosphites/phosphines were downfield shifted
by ꢀ10 ppm. Therefore, these reactions were closely moni-
tored by the 31P NMR technique. The results indicated that
the steric factor dominated the COD displacement reactions.
In view of the cone angles of P(OEt)3 (109ꢁ), P(OEt)Ph2
(133ꢁ), PPh3 (145ꢁ) and PCy3 (170ꢁ) [7], it is anticipated that
phosphites/phosphines with the cone angles of 6133ꢁ should
be able to displace the COD in 1.
Complex 1 was stable to air and moisture, whereas com-
plex 5 was moisture-sensitive. The color changed from yel-
low to green upon the exposure of 5 to air for a few minutes.
In fact, recrystallization of 5 from a wet CH2Cl2/THF solu-
tion gave [{g5:r-Me2C(C5H4)(C2B10H10)}Ru(l-H2O)]2 Æ
2THF (9 Æ 2THF) as green crystals in 56% isolated yield.
The labile nature of coordinated monoamine ligands in 4
and 5 prompted us to further examine the ligand exchange
reactions between 5 and other Lewis bases that could not be
introduced directly from 1.
Treatment of 5 with 2 equiv. of PR3 (R = Ph, Cy) in
refluxing THF afforded mono-substituted complexes
[g5:r-Me2C(C5H4)(C2B10H10)]Ru(NH2Prn)(PPh3) (10) and
[g5:r-Me2C(C5H4)(C2B10H10)]Ru(NH2Prn)(PCy3) (11) in
82% isolated yield, respectively. The complete displacement
of amines was not possible even under forced reaction con-
ditions. On the other hand, 5 reacted with excess P(OEt)3 to
give di-substituted complex 2. These results again suggested
that the steric factor played a crucial role in these displace-
ment reactions (see Scheme 2).
Complex 5 reacted also with excess TMEDA in refluxing
THF afforded [g5:r-Me2C(C5H4)(C2B10H10)]Ru(TMEDA)
(12) in 77% isolated yield. Complex 12 was not accessible
from the reaction of 1 with excess TMEDA. An acetonitrile
coordinated complex [g5:r-Me2C(C5H4)(C2B10H10)]Ru-
(NCCH3)2 (13) was isolated in 93% isolated yield by stirring
a CH3CN solution of 5 at room temperature for 2 days.
Complex 13 reacted readily with 2 equiv. of nPrNH2 in tolu-
ene at room temperature to give 5 quantitatively. It was
noted that there was no reaction between 1 and CH3CN even
at high temperatures. Complex 13 was extremely moisture-
sensitive and converted into 9 as a green compound upon
exposure to air. These ligand exchange reactions showed that
the lability of complexes followed the order: 13 > 5 > 1. The
presence of amine and acetonitrile in complexes 5 and 13
allowed the introduction of new ligands on the ruthenium
site, which is not accessible directly from 1. In this regards,
complexes 5 and 13 may be good candidates as catalyst
precursors.
Unprecedented isolation of a small amount of [g5:r-
Me2C(C5H4)(C2B10H10)]Ru(NH2Prn)2 from an attempted
catalytic reaction of PhC„CH with nPrNH2 in the presence
of 1 prompted us to examine the reaction of 1 with amines.
Treatment of 1 with a large excess amount of amines in
THF at room temperature afforded the COD displacement
complexes [g5:r-Me2C(C5H4)(C2B10H10)]Ru[NH2CH2CH2-
Pri]2 (4), [g5:r-Me2C(C5H4)(C2B10H10)]Ru(NH2Prn)2 (5),
[g5:r-Me2C(C5H4)(C2B10H10)]Ru(g2-NH2CH2CH2NH2)
(6) and [g5:r-Me2C(C5H4)(C2B10H10)]Ru[g2-NH(CH3)-
CH2CH2NH(CH3)] (7), respectively, in 82–88% isolated
yields (Scheme 1). Complex 1 reacted also with two equiv.
of 1,3,4,5-tetramethylimidazol-2-yilidene (NHC) in reflux-
ing THF to produce [g5:r-Me2C(C5H4)(C2B10H10)]Ru-
[NHC]2 (8) in 70% isolated yield.
Complexes 2–8 were soluble in THF, CH2Cl2, toluene
and benzene, but insoluble in n-hexane. Complexes 4 and
5 were moisture-sensitive, whereas 2, 3, 6–8 were air- and
1
moisture-stable. The H NMR experiments showed that
both 4 and 5 reacted rapidly with 1 equiv. of COD in
C6D6 at room temperature to give 1 quantitatively, indicat-
ing that the reactions of 1 with RNH2 were reversible.
Therefore, a large excess amount of RNH2 was necessary

Y. Sun et al. / Journal of Organometallic Chemistry 691 (2006) 3071–3082
3073
P(OEt)3
P(OEt)3
Me
Me
2 P(OEt)3
Ru
C
C
2
PPh2(OEt)
PPh2(OEt)
Me
Me
2 Ph2P(OEt)
Ru
3
NH2CH2CH2Pri
NH2CH2CH2Pri
2 H2N(CH2)2Pri
Me
Me
Ru
C
4
NH2Prn
NH2Prn
Me
Me
Me
Me
2 H2NPrn
Ru
Ru
C
C
C
C
5
1
H2N
H2N
H2
N
Me
Me
Ru
N
H2
6
CH3
NH
MeHN
MeHN
Me
Me
Ru
NH
CH3
7
N
N
2
N
N
Me
Me
Ru
C
N
N
8
Scheme 1.
The 1H NMR spectrum of 9 showed only the resonances
of the linked cyclopentadienyl–carboranyl ligand which
was quite different from its parent complex 5. Four multi-
plets of the Cp protons in the range 4.45–3.24 ppm, two
singlets of the Me2C protons at dH = 1.50 and 1.45 ppm,
one set of PR3 (R = Ph, Cy) and one set of nPrNH2 protons
were observed in the 1H NMR spectra of 10 and 11, respec-
tively. One 31P resonance was also observed in each of
them. On the other hand, the H NMR spectra of 12 and
1
13 exhibited only two multiplets and one singlet for the
linked ligand and one set of the coordinated Lewis base
protons, TMEDA in 12 or CH3CN in 13, supporting the
Cs symmetry of these complexes in solution. The 13C
1
NMR spectra of 9–13 were line with their H NMR data.

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Y. Sun et al. / Journal of Organometallic Chemistry 691 (2006) 3071–3082
Me
Me
Me
Me
2 H2O
Ru
Ru
C
C
O
O
H2
H2
9
PPh3
Me
Me
PPh3
Ru
C
C
NH2Prn
10
PCy3
NH2Prn
NH2Prn
Me
Me
PCy3
Me
Me
Ru
Ru
2 H2O
NH2Prn
C
11
5
Me
Me
Me
N
N
Me
TMEDA
Ru
C
Me
Me
12
NCCH3
NCCH3
Me
Me
2 CH3CN
Ru
C
13
Scheme 2.
2.3. Molecular structures
Single-crystal X-ray analyses confirmed the molecular
structures of 2, 3, 5–10, 12 and 13, shown in Figs. 1–10,
respectively. Table 1 compiled their key structural data.
Except for 9, they all adopt monomeric structures in which
the Ru atom is g5-bound to one cyclopentadienyl ring, r-
bound to one cage carbon atom and coordinated to two
monodentate ligands or one bidentate ligand in a dis-
torted-tetrahedral geometry. The following trends were
observed after carefully examining the bond distances
and angles: (1) the sterically demanding ligands are associ-
ated with the longer Ru–C(cage), Ru–C(ring) and Ru–X
distances, the larger bite angles of X–Ru–X and the smaller
Cent–Ru–C(cage) angles and (2) the variations of C(ring)–
C(bridge)–C(cage) angles are very small within 2ꢁ.
The average Ru–C(cage), Ru–C(ring) and Ru–Cent dis-
tances and C(ring)–C(bridge)–C(cage) angles listed in Table 1
are very comparable to the corresponding values observed
in 1 and other [g5:r-Me2C(C5H4)(C2B10H10)]Ru(P–P) com-
plexes (P–P = bidentate phosphines) [6]. The average Ru–P
Fig. 1. Molecular structure of [g5:r-Me2C(C5H4)(C2B10H10)]Ru[P(OEt)3]2
(2).

Y. Sun et al. / Journal of Organometallic Chemistry 691 (2006) 3071–3082
3075
Fig. 4. Molecular structure of [g5:r-Me2C(C5H4)(C2B10H10)]Ru(g2-
NH2CH2CH2NH2) (6).
Fig. 2. Molecular structure of [g5:r-Me2C(C5H4)(C2B10H10)]Ru[PPh2-
(OEt)]2 (3).
Fig. 5. Molecular structure of [g5:r-Me2C(C5H4)(C2B10H10)]Ru[g2-NH-
(CH3)CH2CH2NH(CH3)] (7).
Fig. 3. Molecularstructureof [g5:r-Me2C(C5H4)(C2B10H10)]Ru(NH2Prn)2
(5).
than the Ru–N (amines) distances, but is close to the corre-
sponding values found in Ru(MeCN)(PiPr3)(‘N2Me2S2’)
(‘N2Me2S2’ = 1,2-ethanediamine-N,N0-bis(2-benzenethio-
˚
late)) (1.990(3) A) [9a] and Ru(C10H8N2S)2(CH3CN)2(BF4)2
0
˚
˚
˚
distances of 2.240(1) A in 2, 2.284(1) A in 3 and 2.328(2) in 10
are close to the corresponding values found in [g5:r-
Me2C(C5H4)(C2B10H10)]Ru(P–P) complexes [6]. The aver-
(C10H8N2S = di-2-pyridyl sulfide-N,N ) (2.022(2) A) [9b].
˚
The average Ru–C (NHC) distance of 2.073(4) A in 8 is
almost identical with that of 2.040(3) A in RuCl2 [g1-
˚
age Ru–N (amines) distances (2.177(2)–2.279(1) A) are very
CN{g6-C6H2Me3-2,4, 6}CH2CH2N(CH2C6H2Me3-2,4,6)]
˚
and 2.086(3) A in RuCl2{g1-CN(CH2C6H2Me3-2,4,6)
˚
comparable to the corresponding values observed in RuCl2-
˚
(COD)[Et(H)NCH2CH2N(H)Et] (2.195(2) A) [8a], RuCl2-
CH2CH2N(CH2CH2OMe)}(C6Me6) [10].
˚
˚
˚
(COD)(C6H15N)2 (2.174(3) A) [8b] and RuCl2(dppp)
Complex 9 is a dinuclear species with a Ru–Ru distance of
˚
(H2NCH2CH2NH2) (2.174(2) A) [8c]. The average Ru–N
2.657(1) A (Fig. 7). Comparing this measured value with the
˚
(CH3CN) distance of 2.068(4) A in 13 is significantly shorter
Ru–Ru single bond distances of 2.773(1) A in (Ph3P)4Ru2(l-

3076
Y. Sun et al. / Journal of Organometallic Chemistry 691 (2006) 3071–3082
Fig. 8. Molecular structure of [g5:r-Me2C(C5H4)(C2B10H10)]Ru-
(NH2Prn)(PPh3) (10) (the solvated toluene molecule is not shown).
Fig. 6. Molecular structure of [g5:r-Me2C(C5H4)(C2B10H10)]Ru{C[N-
(Me)C(Me)@C(Me)N(Me)]}2 (8).
Fig. 7. Molecular structure of [{g5:r-Me2C(C5H4)(C2B10H10)}Ru(l-
H2O)]2 (9) (the solvated THF molecules are not shown).
Fig. 9. Molecular structure of [g5:r-Me2C(C5H4)(C2B10H10)]Ru-
(TMEDA) (12).
H)2(l-CF3SO2)(CO)2HC(SO2CF3)2 Æ CH2Cl2 [11a] and
˚
2.637(1) A in (Me3P)4Ru(l-CH2)2Ru(l-CH2)2Ru(Me3P)4-
to the corresponding values observed in the complexes con-
taining [g5:r-Me2C(C5H4)(C2B10H10)]Ru(II) moiety [6].
The above data all support 9 to be a divalent Ru aqueous
complex.
(BF4)2 [11b], it is better to describe the Ru–Ru interaction
in 9 to be the single bond. The Ru–O distances in 9
(2.063(3), 2.070(3), 2.097(3) and 2.116(3) A) are very
˚
comparable to the Ru–OH2 distances of 2.149(3) and
˚
2.185(3) A in Ru2(C2H5)2(CO)4(H2O)4(CF3SO3)2, 2.100(5)
2.4. Electrochemistry
˚
˚
A in Ru(CO)3(H2O)3(BF4)2 [12a] and 2.050(4) A in
OEt(H2O)Ru(l-O)2Ru (OH2)LOEt (LOEt = CpCo{(EtO)2-
L
For all complexes (except for 9), the electrochemical
study revealed that all observed redox processes were
one-electron and reversible processes at the scan rate of
100 mV sꢁ1, as indicated by the (iPa/iPc) ratios of unity
and the DEp peak separations in the range 86–118 mV.
The redox potentials E1/2 given relative to ferrocenium/fer-
rocene were compiled in Table 2.
P@O}3) [12b]. These measured values are significantly longer
˚
than the Ru–O (oxo) distances, e.g. 1.940(9) A in (py)2-
˚
RuO2(l-O)2RuO2(py)2 (py = pyridine) [13a], 1.887(4) A in
˚
L
OEt(O)Ru(l-O)2Ru(O)LOEt [12b] and 1.733(6) A in (CH2-
SiMe3)3Ru(l-O)2Ru(CH2SiMe3)3 [13b]. As shown in Table 1,
the Ru–C(cage) and Ru–C(ring) distances in 9 are very close

Y. Sun et al. / Journal of Organometallic Chemistry 691 (2006) 3071–3082
3077
Table 2
a
Redox potentials of ruthenium complexes in CH2Cl2
Complex
E1/2 (RuIII/RuII) (V)
DEp (mV)
2
3
0.305
0.213
112
115
118
86
96
108
88
115
102
90
4
ꢁ0.360
ꢁ0.352
ꢁ0.337
ꢁ0.198
ꢁ0.630
0.010
ꢁ0.052
ꢁ0.199
ꢁ0.013
5
6
7
8
10
11
12
13
a
117
All potentials were given relative to ferrocenium/ferrocene. Pt working
electrode: 100 mV sꢁ1; recorded in CH2Cl2 with n-Bu4NPF6 (0.15 M) as
supporting electrolyte.
sized via ligand substitution reactions and fully character-
ized. They are all 18-electron species with a distorted-
tetrahedral geometry. The ruthenium–amine complexes
are much more labile than the ruthenium–COD ones.
For example, 5 is able to react with PR3 (R = Ph, Cy)
and CH3CN, but the COD in 1 is replaced only by phosph-
ites/phosphines ligands with small cone angles. The less
labile complex 1 derived from the classical source of ruthe-
nium moiety [RuCl2(COD)]x stands as a key precursor in
this Cp–carboranyl ruthenium series. Thus it seems that
monoamine and acetonitrile derivatives 5 and 13 constitute
substitution intermediates that cannot be overlooked.
The electrochemical studies indicate that the electron
richness of the Ru atom decreases in the order
L2Ru(NHC)2 >L2Ru(amine)2 >L2Ru(NCMe)2 >L2Ru(P)2.
This work also offers useful information for further inves-
tigation of this novel class of ruthenium carborane com-
plexes in both stoichiometric and catalytic reactions.
Fig. 10. Molecular structure of [g5:r-Me2C(C5H4)(C2B10H10)]Ru-
(NCCH3)2 (13).
All complexes have similar molecular structures with dif-
ferent N- and/or P-ligands or NHC carbenes, thus allowing
us to compare the electron-donating ability of the ligands. As
shown in Table 2, the electron richness of the Ru atom
decreases in the order L2Ru(NHC)2 > L2Ru(amine)2 ꢂ
L2Ru(amine)(phosphine) > L2Ru(NCMe)2 > L2Ru(P)2. This
trend reflects the net results of the two contrary interactions
of r-donation and p-acception. It is noteworthy that the
most electron-rich complex is 8, due to the fact that NHC
carbene exhibits a remarkably strong electron-donating
power [14]. It is also obvious that the primary amine com-
plexes (4, 5, 6) are more electron-rich than the secondary
and tertiary amine complexes 7 and 12. As the most labile
complexes are shown to be 4, 5 and 13, it is suggested that
high reactivity of those complexes is not due to electron-rich-
ness (oxidability) of the Ru metal center, but rather to the
monodentate and labile nature of the ligands.
4. Experimental
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. THF and n-hexane were freshly distilled from sodium
benzophenone ketyl immediately prior to use. CH2Cl2 was
3. Conclusion
A series of ruthenium complexes containing carbon-
bridged carboranyl–cyclopentadienyl ligands were synthe-
Table 1
a
˚
Selected bond distances (A) and angles (ꢁ) for 2, 3, 5–10, 12 and 13
Complex
Ru–Ccage
Average Ru–Cring
Ru–Cent
Average Ru–X
X–Ru–X
Cring–Cbridge–Ccage
Cent–Ru–Ccage
2
3
5
6
7
8
9
2.142(1)
2.167(3)
2.095(5)
2.098(2)
2.102(3)
2.149(4)
2.141(4)
2.150(5)
2.105(6)
2.230(1)
2.232(3)
2.142(6)
2.149(2)
2.157(3)
2.220(4)
2.204(5)
2.206(5)
2.207(6)
1.882
1.876
1.771
1.773
1.785
1.864
1.841
1.843
1.833
2.240(1) (X = P)
2.284(1) (X = P)
2.204(5) (X = N)
2.177(2) (X = N)
2.185(3) (X = N)
2.073(4) (X = C)
2.084(3) (X = O)
2.090(3) (X = O)
2.176(5) (X = N)
2.328(2) (X = P)
2.268(3) (X = N)
2.068(4) (X = N)
93.6(1)
95.8(1)
83.5(2)
78.1(1)
78.9(1)
88.1(2)
80.0(1)
79.8(1)
89.3(2)
109.2(1)
109.4(2)
108.8(4)
109.4(1)
109.2(2)
109.6(3)
108.0(4)
109.2(4)
107.9(5)
115.0
113.8
120.1
120.3
119.2
115.2
110.9
111.2
116.3
10
12
13
a
2.217(3)
2.111(5)
2.171(4)
2.166(6)
1.798
1.799
77.4(1)
83.3(2)
109.2(3)
109.7(4)
117.0
118.7
Cent: the centroid of the cyclopentadienyl ring.

3078
Y. Sun et al. / Journal of Organometallic Chemistry 691 (2006) 3071–3082
freshly distilled from CaH2 and P2O5, respectively, immedi-
ately prior to use. [g5:r-Me2C(C5H4)(C2B10H10)]Ru(COD)
[6] and 1,3,4,5-tetramethylimidazol-2-ylidene [15] were pre-
pared according to the literature methods. All other chemi-
cals were purchased from either Aldrich or Acros
Chemical Co. and used as received unless otherwise noted.
Cyclic voltammetric measurements were performed using a
BAS CV-50 W Voltammetric Analyzer. The electrochemical
cell comprised a platinum-wire working electrode, a silver-
wire reference electrode, and a platinum-disk counter elec-
trode. All measurements were made in a dry N2 atmosphere.
All sample solutions (CH2Cl2) contained n-Bu4NPF6
(0.15 M) as supporting electrolyte and complex
(2.0 · 10ꢁ3 M). Chemical potentials were internally refer-
enced to the ferrocenium/ferrocene redox system. Infrared
spectra were obtained from KBr pellets prepared in the
glovebox on a Perkin–Elmer 1600 Fourier transform spec-
trometer. 1H and 13C NMR spectra were recorded on a Bru-
ker DPX 300 spectrometer at 300 and 75 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 Æ OEt2
(0.0 ppm) for boron chemical shifts, and to external 85%
H3PO4 (0.0 ppm) for phosphorus chemical shifts. Elemental
analyses were performed by MEDAC Ltd. UK or Shanghai
Institute of Organic Chemistry, CAS, China. Melting points
were determined on an Electrothermal Digital Melting Point
Apparatus M-IA9100 and were uncorrected.
mmol) and ethyl diphenylphosphinite (0.23 g, 1.0 mmol)
in THF (15 mL) using the identical procedures reported
for 2: yield 0.33 g (81%), mp 269 ꢁC dec. H NMR (C6D6,
1
d/ppm): d 7.56–7.03 (m, 20H, Ph), 4.13 (m, 2H, C5H4),
3.72 (m, 2H, C5H4), 3.23 (m, 2H, OCH2), 3.07 (m, 2H,
OCH2), 1.32 (s, 6H, C(CH3)2), 0.99 (t, J = 6.9 Hz, 6H,
CH2CH3). 13C{1H} NMR (C6D6, d/ppm): d 139.3, 139.1,
136.3, 133.2, 132.3, 129.9, 129.7, 127.4 (aryl C), 84.2, 77.0
(C5H4), 63.8 (OCH2), 39.7 (C(CH3)2), 31.7 (C(CH3)2),
16.1 (CH2CH3). 31P{1H} NMR (C6D6, d/ppm): d 135.4.
11B{1H} NMR (C6D6, d/ppm): d ꢁ3.4 (2B), ꢁ7.3 (8B). IR
(KBr, cmꢁ1): m 3051w, 2970m, 2584vs, 2526vs, 1631w,
1438m, 1380m, 1091s, 1025vs, 929s, 740m, 694s. Anal. Calc.
for C38H50B10O2P2Ru: C, 56.35; H, 6.22. Found: C, 56.42;
H, 6.77%.
4.3. Preparation of [g5:r-Me2C(C5H4)(C2B10H10)]Ru-
[NH2CH2CH2Pri]2 (4)
A
THF solution (10 mL) of [g5:r-Me2C(C5H4)-
(C2B10H10)]Ru(COD) (1; 0.23 g, 0.50 mmol) and isopentyl-
amine (0.44 g, 5.0 mmol) were mixed at room temperature
and stirred for 48 h. After removal of THF and excess
isopentylamine, the resulting solid was washed with n-hex-
ane. Recrystallization from THF at room temperature gave
4 as a yellow crystalline solid (0.23 g, 88%), mp 197 ꢁC dec.
1H NMR (C6D6, d/ppm): d 3.85 (m, 2H, C5H4), 2.95 (m,
2H, C5H4), 2.53 (m, 2H, CH2), 2.35 (m, 2H, CH2), 2.09 (m,
2H, CH2), 1.46 (s, 6H, C(CH3)2), 1.32 (m, 2H, CH2), 0.98
(m, 2H, CH), 0.78 (d, J = 3.0 Hz, 12H, CH(CH3)2).
13C{1H} NMR (C6D6, d/ppm): d 90.3, 75.1 (C5H4), 49.7,
43.1 (CH2), 42.0 (C(CH3)2), 32.5 (C(CH3)), 26.3 (CH),
23.1, 22.9 (CH(CH3)2). 11B{1H} NMR (C6D6, d/ppm): d
ꢁ3.8 (2B), ꢁ6.4 (4B), ꢁ8.1 (2B), ꢁ12.9 (2B). IR (KBr,
cmꢁ1): m 3301m, 2943s, 2557vs, 1589m, 1454m, 1367m,
1058m, 796w. Anal. Calc. for C20H46B10N2Ru: C, 45.86;
H, 8.85; N, 5.35. Found: C, 45.51; H, 9.00; N, 5.37%.
4.1. Preparation of [g5:r-Me2C(C5H4)(C2B10H10)]-
Ru[P(OEt)3]2 (2)
A THF solution (10 mL) containing [g5:r-Me2C(C5H4)-
(C2B10H10)]Ru(COD) (1; 0.23 g, 0.50 mmol) and triethyl
phosphite (0.17 g, 1.0 mmol) was heated to reflux for
48 h. After removal of THF, the resulting solid was washed
with n-hexane. Recrystallization from THF (10 mL) at
room temperature gave 2 as pale yellow crystals (0.29 g,
4.4. Preparation of [g5:r-Me2C(C5H4)(C2B10H10)]Ru-
(NH2Prn)2 (5)
1
85%), mp 199–200 ꢁC. H NMR (C6D6, d/ppm): d 4.88
(m, 2H, C5H4), 4.37 (m, 2H, C5H4), 3.81 (m, 12H,
OCH2), 1.51 (s, 6H, C(CH3)2), 1.09 (t, J = 7.2 Hz, 18H,
CH2CH3). 13C{1H} NMR (C6D6, d/ppm): d 80.4, 76.8
(C5H4), 60.6 (OCH2), 40.0 (C(CH3)2), 31.7 (C(CH3)2),
16.2 (CH2CH3). 31P{1H} NMR (C6D6, d/ppm): d148.2.
11B{1H} NMR (C6D6, d/ppm): d ꢁ2.3 (2B), ꢁ5.8 (3B),
ꢁ7.2 (3B), ꢁ8.6 (2B). IR (KBr, cmꢁ1): m 2977vs, 2933s,
2898s, 2584vs, 2537vs, 1442m, 1384s, 1259w, 1044vs,
939vs, 762s. Anal. Calc. for C22H50B10O6P2Ru: C, 38.76;
H, 7.39. Found: C, 38.50; H, 7.35%.
This complex was prepared from [g5:r-Me2C(C5H4)-
(C2B10H10)]Ru(COD) (1; 0.23 g, 0.50 mmol) and propyl-
amine (0.30 g, 5.0 mmol) in THF (15 mL) using the
identical procedures reported for 4: yield 0.19 g (82%),
1
mp 185 ꢁC dec. H NMR (C6D6, d/ppm): d 3.79 (m, 2H,
C5H4), 2.98 (m, 2H, C5H4), 2.39 (m, 2H, CH2), 2.17 (m,
2H, CH2), 1.46 (s, 6H, C(CH3)2), 1.02 (m, 4H, CH2),
0.63 (t, J = 7.2 Hz, 6H, CH3). 13C{1H} NMR (C6D6, d/
ppm): d 76.0, 74.4 (C5H4), 54.9, 52.6 (CH2), 41.5
(C(CH3)2), 32.0 (CH3), 26.8 (CH2), 11.0 (CH3). 11B{1H}
NMR (C6D6, d/ppm): d ꢁ4.0 (2B), ꢁ6.6 (4B), ꢁ8.0
(2B), ꢁ13.1 (2B). IR (KBr, cmꢁ1): m 3315s, 3261w,
2961s, 2871m, 2544vs, 1584s, 1461m, 1380m, 1259m,
1041s, 804s, 742w. Anal. Calc. for C16H38B10N2Ru: C,
41.09; H, 8.19; N, 5.99. Found: C, 41.25; H, 8.15; N,
6.00%.
4.2. Preparation of [g5:r-Me2C(C5H4)(C2B10H10)]-
Ru[PPh2(OEt)]2 (3)
This complex was prepared as yellow crystals from
[g5:r-Me2C(C5H4)(C2B10H10)]Ru(COD) (1; 0.23 g, 0.50

Y. Sun et al. / Journal of Organometallic Chemistry 691 (2006) 3071–3082
3079
4.5. Preparation of [g5:r-Me2C(C5H4)(C2B10H10)]Ru(g2-
NH2CH2CH2NH2) (6)
4.8. Preparation of [{g5:r-Me2C(C5H4)(C2B10H10)}Ru(l-
H2O)]2 Æ 2THF (9 Æ 2THF)
This complex was prepared as yellow crystals from [g5:r-
Me2C(C5H4)(C2B10H10)]Ru(COD) (1; 0.23 g, 0.50 mmol)
and 1,2-diaminoethane (0.30 g, 5.0 mmol) in THF (15 mL)
using the identical procedures reported for 4: yield 0.18 g
Recrystallization of 5 (100 mg, 0.19 mmol) from wet
CH2Cl2/THF (1:1, 4 mL) in air give 9 Æ 2THF as green crys-
tals (57 mg, 56%), mp 154 ꢁC dec. 1H NMR ([D5]pyridine, d/
ppm): d 5.36 (m, 2H, C5H4), 5.17 (m, 2H, C5H4), 4.96 (m, 4H,
C5H4), 3.63 (m, 8H, THF), 1.61 (m, 8H, THF), 1.52 (s, 12H,
C(CH3)2). 13C{1H} NMR ([D5]pyridine, d/ppm): d 83.2,
79.6 (C5H4), 42.3 (C(CH3)2), 32.5, 31.6 (CH3). 11B{1H}
NMR ([D5]pyridine, d/ppm): d ꢁ3.2 (4B), ꢁ4.6 (4B), ꢁ8.1
(12B). IR (KBr, cmꢁ1): m 3490m, 3081w, 2966w, 2561vs,
2341w, 1631w, 1461w, 1384m, 1041m, 845m, 744m. Anal.
Calc. for C28H60B20O4Ru2 Æ (9 + 2THF): C, 38.25; H, 6.88.
Found: C,38.26; H, 6.85%.
1
(88%), mp 133–134 ꢁC. H NMR (C6D6, d/ppm): d 3.57
(m, 2H, C5H4), 3.26 (m, 2H, C5H4), 2.40 (m, 4H, CH2),
1.50 (s, 6H, C(CH3)2). 13C{1H} NMR (C6D6, d/ppm): d
72.3 (C5H4), 56.1 (CH2), 43.9 (C(CH3)2), 32.0 (CH3).
11B{1H} NMR (C6D6, d/ppm): d ꢁ4.3 (2B), ꢁ7.0 (4B),
ꢁ8.9 (2B), ꢁ12.2 (2B). IR (KBr, cmꢁ1): m 3322vs, 2930s,
2579vs, 2536vs, 1582vs, 1452s, 1360m, 1185w, 1025s,
863m, 800s, 742m. Anal. Calc. for C12H28B10N2Ru: C,
35.19; H, 6.90; N, 6.84. Found: C, 34.93; H, 6.92; N, 6.64%.
4.9. Preparation of [g5:r-Me2C(C5H4)(C2B10H10)]Ru-
(NH2Prn)(PPh3) (10 Æ 0.5toluene)
4.6. Preparation of [g5:r-Me2C(C5H4)(C2B10H10)]Ru[g2-
NH(CH3)CH2CH2NH(CH3)] (7)
Triphenylphosphine (0.26 g, 1.00 mmol) was added to a
THF solution (10 mL) of [g5:r-Me2C(C5H4)(C2B10H10)]-
Ru(NH2Prn)2 (5; 0.23 g, 0.50 mmol), and the mixture was
heated to reflux for 24 h. After removal of the solvent,
the residue was recrystallized from THF at room tempera-
ture to give 10 Æ 0.5toluene as yellow crystals (0.29 g, 82%),
This complex was prepared as yellow crystals from
[g5:r-Me2C(C5H4)(C2B10H10)]Ru(COD)
(1;
0.23 g,
0.50 mmol) and N,N0-dimethylethylenediamine (0.44 g,
5.0 mmol) in THF (15 mL) using the identical procedures
reported for 4: yield 0.19 g (87%), mp 264 ꢁC dec. 1H
NMR (C6D6, d/ppm): d 3.66 (m, 2H, C5H4), 3.09 (m,
2H, C5H4), 2.17 (s, 6H, NCH3), 1.64 (m, 4H, CH2), 1.46
(s, 6H, C(CH3)2). 13C{1H} NMR (C6D6, d/ppm): d 75.9
(C5H4), 54.5, 52.8 (NCH2), 46.9 (NCH3), 41.3 (C(CH3)2),
32.0 (CH3). 11B{1H} NMR (C6D6, d/ppm): d ꢁ3.9 (1B),
ꢁ5.7 (1B), ꢁ6.6 (2B), ꢁ7.6 (2B), ꢁ8.5 (2B), ꢁ13.1 (2B).
IR (KBr, cmꢁ1): m 3718w, 3262w, 2966m, 2911m, 2546vs,
1621w, 1457w, 1373w, 1087s, 1038s, 806s. Anal. Calc. for
C14H32B10N2Ru: C, 38.43; H, 7.37; N, 6.40. Found: C,
38.54; H, 7.44; N, 6.29%.
1
mp 155–156 ꢁC. H NMR (C6D6, d/ppm): d 7.40 (m, 6H,
Ph), 7.14 (m, 9H, Ph), 4.45 (m, 1H, C5H4), 3.80 (m, 1H,
C5H4), 3.78 (m, 1H, C5H4), 3.47 (m, 1H, C5H4), 2.42 (m,
2H, CH2), 1.46 (s, 3H, C(CH3)2), 1.45 (s, 3H, C(CH3)2),
0.66 (m, 2H, CH2), 0.34 (t, J = 7.2 Hz, 3H, CH3).
13C{1H} NMR (C6D6, d/ppm): d 133.6, 129.7, 129.3,
125.6, 124.1 (aryl C), 78.5, 67.4, 59.8, 55.5 (C5H4), 40.3
(C(CH3)2), 32.1, 31.2 (C(CH3)2), 27.0 (CH2), 10.4 (CH3).
31P{1H} NMR (C6D6, d/ppm): d58.1. 11B{1H} NMR
(C6D6, d/ppm): d ꢁ2.7 (2B), ꢁ5.3 (2B), ꢁ7.4 (4B), ꢁ11.9
(2B). IR (KBr, cmꢁ1): m 3308s, 3261w, 3046w, 2972s,
2932s, 2571vs, 1579m, 1469m, 1432s, 1180m, 806m, 746s.
Anal. Calc. for C32.75H46B10NPRu Æ (10 + 0.25toluene): C,
56.69; H, 6.75; N, 2.02. Found: C, 56.62; H, 6.62; N, 1.68%.
4.7. Preparation of [g5:r-Me2C(C5H4)(C2B10H10)]Ru-
(NHC)2 (8)
This complex was prepared as red crystals from [g5:r-
Me2C(C5H4)(C2B10H10)]Ru(COD) (1; 0.23 g, 0.50 mmol)
and 1,3,4,5-tetramethylimidazol-2-ylidene (NHC; 0.11 g,
1.0 mmol) in THF (15 mL) using the identical procedures
reported for 2: yield 0.21 g (70%), mp 288 ꢁC dec. 1H
NMR (C6D6, d/ppm): d 5.05 (m, 1H, C5H4), 4.21 (m,
1H, C5H4), 4.20 (m, 1H, C5H4), 3.44 (m, 1H, C5H4),
4.07, 3.44, 2.51, 2.26 (s, s, s, s, 12H, C(CH3) of NHC),
1.78 (s, 3H, C(CH3)2), 1.59 (s, 3H, C(CH3)2), 1.65, 1.63,
1.45, 1.44 (s, s, s, s, 12H, N(CH3) of NHC). 13C{1H}
NMR (C6D6, d/ppm): d 189.9 (Ru@C), 83.3, 76.2 (C5H4),
67.3, 67.0 (C@C), 39.8 (C(CH3)2), 36.1, 35.7 (C(CH3)2),
34.6, 34.4, 32.2, 32.0 (NCH3), 9.7, 9.5, 9.4, 9.2 (CH3C@C).
11B{1H} NMR (C6D6, d/ppm): d ꢁ3.4 (2B), ꢁ5.9 (4B),
ꢁ7.9 (4B). IR (KBr, cmꢁ1): m 2981w, 2952w, 2919w,
2534vs, 2354m, 2269m, 1554w, 1382m, 1261w, 1091m,
1031w, 800m. Anal. Calc. for C24H44B10N4Ru: C, 48.22;
H, 7.42; N, 9.37. Found: C, 48.75; H, 7.42; N, 9.26%.
4.10. Preparation of [g5:r-Me2C(C5H4)(C2B10H10)]Ru-
(NH2Prn)(PCy3) (11)
This complex was prepared as yellow crystals from [g5:r-
Me2C(C5H4)(C2B10H10)]Ru(Prn)2 (5; 0.23 g, 0.50 mmol) and
tricyclohexylphosphine (0.28 g, 1.00 mmol) in THF (15 mL)
using the identical procedure reported for 10: yield 0.28 g
(82%), mp 166 ꢁC dec. 1H NMR (C6D6, d/ppm): d 4.32 (m,
1H, C5H4), 4.14 (m, 1H, C5H4), 3.87 (m, 1H, C5H4), 3.24
(m, 1H, C5H4), 2.67 (m, 2H, CH2), 2.02–1.05 (m, 35H,
Cy + CH2), 1.50 (s, 3H, C(CH3)2), 1.46 (s, 3H, C(CH3)2),
0.68 (t, J = 7.2 Hz, 3H, CH3). 13C{1H} NMR (C6D6, d/
ppm): d 82.0, 73.9, 65.1 (C5H4), 39.0 (C(CH3)2), 31.1, 30.8
(C(CH3)2), 27.9, 27.8, 27.5 (Cy), 27.0 (NH2CH2), 11.0
(CH2CH3). 31P{1H} NMR (C6D6, d/ppm): d 36.8. 11B{1H}
NMR (C6D6, d/ppm): d ꢁ4.2 (2B), ꢁ6.1 (2B), ꢁ8.1 (2B),
ꢁ9.9 (2B), ꢁ13.1 (2B). IR (KBr, cmꢁ1): m 3281w, 2925vs,

3080
Y. Sun et al. / Journal of Organometallic Chemistry 691 (2006) 3071–3082
2844vs, 2549vs, 1585m, 1446s, 1261w, 1043m, 804m. Anal.
Calc. for C31H62B10NPRu: C, 54.04; H, 9.07; N, 2.03.
Found: C, 54.13; H, 8.97; N, 2.07%.
4.11. Preparation of [g5:r-Me2C(C5H4)(C2B10H10)]Ru-
(TMEDA) (12)
This complex was prepared as red crystals from [g5:r-
Me2C(C5H4)(C2B10H10)]Ru(NH2Prn)2 (5; 0.23 g, 0.50
mmol)
and
N,N,N0,N0-tetramethylethylenediamine
(TMEDA; 0.12 g, 1.0 mmol) in THF (15 mL) using the iden-
tical procedures reported for 10: yield 0.18 g (77%), mp
1
240 ꢁC dec. H NMR (CD2Cl2, d/ppm): d 3.90 (m, 2H,
C5H4), 3.38 (m, 2H, C5H4), 3.10 (s, 6H, NCH3), 3.00 (s,
6H, NCH3), 2.43 (m, 4H, NCH2), 1.37 (s, 6H, C(CH3)).
13C{1H} NMR (CD2Cl2, d/ppm): d 75.1 (C5H4), 61.5, 60.5
(NCH2), 54.6, 51.9 (NCH3), 39.3 (C(CH3)2), 31.8
(C(CH3)2). 11B{1H} NMR (CD2Cl2, d/ppm): d ꢁ7.7 (2B),
ꢁ9.4 (2B), ꢁ10.7 (2B), ꢁ12.3 (4B). IR (KBr, cmꢁ1): m
3316m, 2958vs, 2877s, 2549vs, 1585m, 1457m, 1376m,
1044s, 806m, 744w. Anal. Calc. for C16H36B10N2Ru: C,
41.27; H, 7.79; N, 6.02. Found: C, 41.14; H, 7.76; N, 6.11%.
4.12. Preparation of [g5:r-Me2C(C5H4)(C2B10H10)]Ru-
(NCCH3)2 (13)
A CH3CN solution (10 mL) of [g5:r-Me2C(C5H4)-
(C2B10H10)]Ru(NH2Prn)2 (5; 0.23 g, 0.50 mmol) was stirred
at room temperature for 48 h. After removal of CH3CN,
the resulting solid was washed with n-hexane. Recrystalli-
zation from CH3CN at room temperature gave 13 as yel-
low crystals (0.20 g, 93%), mp 188 ꢁC dec. 1H NMR
(C6D6, d/ppm): d 4.44 (m, 2H, C5H4), 3.67 (m, 2H,
C5H4), 1.49 (s, 6H, C(CH3)2), 0.92 (s, 6H, CH3CN).
13C{1H} NMR (C6D6, d/ppm): d 122.2 (CH3CN), 77.7,
61.7 (C5H4), 41.6 (C(CH3)2), 31.9 (C(CH3)2), 2.4 (CH3).
11B{1H} NMR (C6D6, d/ppm): d ꢁ3.6 (2B), ꢁ6.7 (2B),
ꢁ7.9 (2B), ꢁ9.1 (2B), ꢁ10.5 (2B). IR (KBr, cmꢁ1): m
3448vs, 2927vs, 2556vs, 2270s, 1658w, 1454s, 1349s,
1060s, 802w. Anal. Calc. for C14H26B10N2Ru: C, 38.97;
H, 6.07; N, 6.49. Found: C, 39.15; H, 6.21; N, 6.58%.
4.13. 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 either a Bruker SMART 1000 CCD
diffractometer or an MSC/Rigaku RAXIS-II imaging plate
using Mo Ka radiation. An empirical absorption correc-
tion was applied using the SADABS program [16]. All struc-
tures were solved by direct methods and subsequent
Fourier difference techniques and refined anisotropically
for all non-hydrogen atoms by full-matrix least-squares
calculations on F2 using the SHELXTL program package
[17]. All hydrogen atoms were geometrically fixed using
the riding model. Complexes 9 and 10 showed two THF
and half toluene of solvation, respectively. The solvated

Y. Sun et al. / Journal of Organometallic Chemistry 691 (2006) 3071–3082
3081
Table 4
Crystal data and summary of data collection and refinement for 9, 10, 12 and 13
Complex
9 Æ 2THF
10 Æ 0.5toluene
12
13
Formula
C28H60B20O4Ru2
0.50 · 0.50 · 0.40
879.1
C34.5H48B10NPRu
0.50 · 0.40 · 0.30
716.9
C16H36B10N2Ru
0.50 · 0.30 · 0.20
465.6
Monoclinic
P21/c
13.694(3)
10.729(2)
C14H26B10N2Ru
0.50 · 0.30 · 0.20
431.5
Orthorhombic
Pnma
Crystal size (mm)
Formula weight
Crystal system
Space group
Triclinic
Triclinic
ꢀ
ꢀ
P1
P1
˚
a (A)
11.473(2)
12.781(3)
10.598(2)
11.424(2)
14.581(3)
13.474(3)
˚
b (A)
˚
c (A)
16.952(3)
18.652(4)
16.000(3)
10.660(2)
a (ꢁ)
b (ꢁ)
c (ꢁ)
76.88(3)
74.24(3)
77.78(3)
2299.9(8)
83.37(3)
84.72(3)
80.01(3)
2203.0(8)
90
105.55(3)
90
2264.8(8)
90
90
90
2094.2(7)
3
˚
V (A )
Z
2
2
4
4
Dcalc (Mg mꢁ3
)
˚
1.269
Mo Ka (0.71073)
50.0
0.687
1.081
Mo Ka (0.71073)
48.0
0.414
1.366
Mo Ka (0.71073)
51.0
0.698
1.369
Mo Ka (0.71073)
51.0
0.749
872
Radiation (k/A)
2hmax (ꢁ)
l/mmꢁ1
F(000)
896
742
960
Observed reflections
Parameters
Goodness-of-fit on F2
Final R indices [I > 2r(I)]
7173
533
1.221
5044
439
1.281
7225
268
1.074
1933
133
1.196
R1 = 0.053, wR2 = 0.162
R1 = 0.081, wR2 = 0.257
R1 = 0.043, wR2 = 0.130
R1 = 0.046, wR2 = 0.120
[2] (a) B.M. Trost, Acc. Chem. Res. 35 (2002) 695;
toluene molecule in 10 was highly disordered and only
arene ring was located using rigid body refinement. Crystal
data and details of data collection and structure refine-
ments are given in Tables 3 and 4.
´
(b) S. Derien, F. Monnier, P.H. DixneufRuthenium Catalysts in Fine
Chemistry, vol. 5, Springer, Berlin, 2004 (Chapter 1).
´
[3] (a) J.Le. Paih, F. Monnier, S. Derien, P.H. Dixneuf, E. Clot, O.
Eisenstein, J. Am. Chem. Soc. 125 (2003) 11964;
´
(b) J.Le. Paih, S. Derien, C. Bruneau, B. Demerseman, L. Toupet,
Acknowledgments
P.H. Dixneuf, Angew. Chem., Int. Ed. 40 (2001) 2912.
[4] (a) Y. Yamamoto, R. Ogawa, K. Itoh, Chem. Commun. (2000)
549;
This work was supported by grants from the Research
Grants Council of The Hong Kong Special Administration
Region (Project No. CUHK 4026/02P), Mainline Research
Scheme of The Chinese University of Hong Kong (Project
No. MR01/002), and the PROCORE – France/Hong
Kong Joint Research Scheme sponsored by the Research
Grants Council of Hong Kong and the Consulate General
of France in Hong Kong (Reference No. F-HK15/02T).
(b) Y. Yamamoto, K. Hattori, J.I. Ishii, H. Nishiyama, K. Itoh,
Chem. Commun. (2005) 4438;
(c) Y. Yamamoto, T. Arakawa, R. Ogawa, K. Itoh, J. Am. Chem.
Soc. 125 (2003) 12143.
¨
[5] (a) J.Le. Paih, S. De´rien, I. Ozdemir, P.H. Dixneuf, J. Am. Chem.
Soc. 122 (2000) 7400;
(b) F. Monnier, D. Castillo, S. Derien, L. Toupet, P.H. Dixneuf,
Angew. Chem., Int. Ed. 42 (2003) 5474.
´
[6] Y. Sun, H.-S. Chan, P.H. Dixneuf, Z. Xie, Organometallics 23 (2004)
5864.
Appendix A. Supplementary data
[7] M. Hirano, R. Asakawa, C. Nagata, T. Miyasaka, N. Komine, S.
Komiya, Organometallics 22 (2003) 2378.
[8] (a) M.E. Morilla, G. Morfes, M.C. Nicasio, T.R. Belderrain, M.M.
Crystallographic data in CIF format for the structural
analysis has been deposited with the Cambridge Crystallo-
graphic Data Centre, the CCDC reference numbers
289259–289268 for 2, 3, 5–8, 9 Æ 2THF, 10 Æ 0.5toluene, 12
and 13, respectively. Copies of this information may be
obtained free of charge from The Director, CCDC, 12
Union Road, Cambridge, CB2 1EZ, UK (fax: +44 1223
336 033; e-mail: deposit@ccdc.cam.ac.uk or www: http://
www.ccdc.cam.ac.uk). Supplementary data associated with
this article can be found, in the online version, at
doi:10.1016/j.jorganchem.2006.03.022.
´
´
Dıaz-Requejo, C. Graiff, A. Tiripicchio, R. Sanchez-Delgado, P.J.
´
Perez, Chem. Commun. (2002) 1848;
(b) C. Potvin, J.M. Manoli, G. Pannetier, R. Chevalier, N. Platzer, J.
Organomet. Chem. 113 (1976) 273;
(c) E. Lindner, H.A. Mayer, I. Warad, K. Eichele, J. Organomet.
Chem. 665 (2003) 176.
[9] (a) D. Sellmann, B. Hautsch, A. Ro¨sler, F.W. Heinemann, Angew.
Chem., Int. Ed. 40 (2001) 1505;
(b) G. Bruno, F. Nicolo´, G. Tresoldi, S. Lanza, Acta Crystallogr.,
Sect. C 58 (2002) m56.
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[10] B. C¸ etinkaya, S. Demir, I. Ozdemir, L. Toupet, D. Semeril, C.
Bruneau, P.H. Dixneuf, Chem. Eur. J. 9 (2003) 2323.
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