Half-sandwich trihydrido ruthenium complexes

Article abstract of DOI:10.1016/j.jorganchem.2007.07.024

This paper reports facile preparation of half-sandwich trihydrido complexes of ruthenium based on the reactions of the readily available precursors [Cp(R₃P)Ru(NCCH₃)₂][PF₆] with LiAlH₄. The target com

Full text of DOI:10.1016/j.jorganchem.2007.07.024

Journal of Organometallic Chemistry 692 (2007) 5081–5085
www.elsevier.com/locate/jorganchem
Note
Half-sandwich trihydrido ruthenium complexes
a
c
Alexandr L. Osipov , Dmitry V. Gutsulyak a,b, Lyudmila G. Kuzmina ,
d
a
e
a,b,
*
Judith A.K. Howard , Dmitry A. Lemenovskii , Georg Suss-Fink , Georgii I. Nikonov
¨
a
Chemistry Department, Moscow State University, Vorob’evy Gory, 119992 Moscow, Russia
Chemistry Department, Brock University, 500 Glenridge Ave., St. Catharines, ON, Canada L2S 3A1
b
c
Institute of General and Inorganic Chemistry, RAS, Leninskii Prosp. 31, 119991 Moscow, Russia
d
Chemistry Department, University of Durham, South Road, Durham DH1 3LE, UK
Institut de Chimie, Universite´ de Neuchaˆtel, Case Postale 158, CH-2009 Neuchaˆtel, Switzerland, UK
e
Received 24 May 2007; received in revised form 30 June 2007; accepted 1 July 2007
Available online 27 July 2007
Abstract
This paper reports facile preparation of half-sandwich trihydrido complexes of ruthenium based on the reactions of the readily avail-
able precursors [Cp(R3P)Ru(NCCH3)2][PF6] with LiAlH4. The target complexes were characterized by spectroscopic methods and X-ray
structure analysis of CpðPhPri PÞRuH3.
2
ꢀ 2007 Elsevier B.V. All rights reserved.
Keywords: Ruthenium; Hydride
1. Introduction
try. Apart from their potential synthetic utility, ruthenium
trihydrides are also of interest because of their propensity
to manifest quantum-mechanical exchange coupling [13].
Previously, only one trihydride complex with unsubsti-
tuted Cp ring, Cp(Ph3P)RuH3 (1a), has been reported
[14]. By contrast, a family of permethyl substituted com-
plexes Cp*(R3P)RuH3 (Cp*@C5Me5) is well described
[15], including the X-ray structure of Cp*(Ph3P)RuH3
[16]. Complex 1a is a classical trihydride [16], whereas the
isolobal tris(pyrazolyl)borate complex Tp(Ph3P)RuH(g2-
H2) exist in a hydride(dihydrogen) form [17], underpinning
the strong effect of the ring on the extent of Ru–H interac-
tion. Here, we report facile general access to a series of
complexes Cp(R3P)RuH3 (R3P@Ph3P (a), Ph2PriP (b),
PhPri2P (c) and Pri3P (d)) and the crystal structure of com-
plex Cp(Ph2PriP)RuH3.
Half-sandwich complexes of ruthenium find multiple
applications in chemistry as effective catalysts [1] and as
platforms to support unusual metal–ligand and ligand–
ligand bonding [2–5]. Our interest in this field stems from
the observation that the CpLRu fragment (where L is a
two-electron donor) is formally isolobal with the Cp2M
(M = Nb, Ta, Ti), Cp(RN)M (M = V, Nb, Ta) and
(RN)2M (M = Mo, W) moieties [6] which were found to
support a variety of H. . .SiX and H. . .GeCl interligand
interactions [7–10]. Given the fact that Group 5 trihydrides
Cp2MH3 (M = Nb, Ta) are readily available [11] and are
very useful starting points in the chemistry of Group 5 met-
allocenes [12], we expected that ruthenium trihydrides
Cp(R3P)RuH3 would exhibit an analogously rich chemis-
2. Results and discussion
*
Corresponding author. Address: Chemistry Department, Brock Uni-
versity, 500 Glenridge Ave., St. Catharines, ON, Canada L2S 3A1. Tel.:
+1 905 6885550x3350; fax: +1 905 9328846.
Davis et al. previously reported that reaction of
Cp(Ph3P)2RuCl with LiAlH4 in THF affords a 4:1 mixture
E-mail address: gnikonov@brocku.ca (G.I. Nikonov).
0022-328X/$ - see front matter ꢀ 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2007.07.024

5082
A.L. Osipov et al. / Journal of Organometallic Chemistry 692 (2007) 5081–5085
of Cp(Ph3P)RuH3 and Cp(Ph3P)2RuH, from which the for-
mer complex can be isolated by recrystallization from ether
[14]. In our hands, however, difficult-to-separate mixtures
of variable ratios of Cp(Ph3P)RuH3 and Cp(Ph3P)2RuH
were produced. Attempts to extend this approach to the
preparation of other complexes Cp(R3P)RuH3 by reacting
the mixed phosphine precursors Cp(R3P)(Ph3P)RuCl [18]
with LiAlH4 lead to mixtures containing predominantly
the monohydrides Cp(R3P)(Ph3P)RuH.
The related permethyl substituted complexes Cp*-
(R3P)RuH3 (Cp* – pentamethylcyclopentadiene) have been
previously prepared by the reaction of Cp*(R3P)RuCl2 with
NaBH4 in ethanol [15a], with LiBHEt3 in THF [15b] and by
dihydrogen addition to the 16e compound Cp*(R3P)RuOR
[15c]. None of these precursor chloride or alkoxide
compounds are available for the fragment Cp(R3P)Ru yet.
We designed an alternative strategy to the half-sandwich
Ru trihydrides based on the reaction of cationic complexes
[Cp(R3P)Ru(NCCH3)2][PF6] (2a–d) (Scheme 1) with
LiAlH4. The key starting material, the compound [CpRu-
(NCCH3)3][PF6] (3), has recently become available through
Fig. 1. Molecular structure of complex 1b. Selected molecular parameters
(bonds in A, angles in ꢁ): Ru(1)–P(1) 2.2465(4), Ru(1)–H(1) 1.50(3),
the contribution of Kundig et al. [19], which opens a new
¨
˚
facile route to the vast chemistry of the cation
[CpRu(NCCH3)3]+ [1a,20]. Reactions of 3 with an equiva-
lent of phosphine R3P allow for easy preparation of the cor-
responding exchange products [Cp(R3P)Ru (NCCH3)2]
[PF6] (2a–d) characterized by NMR and IR spectroscopy
(Scheme 1) [21]. In particular, the N„C triple bond gives rise
to a band in the IR spectrum at 2276 cmꢀ1, whose position
does not depend on the type of phosphine ligand being
present. Treatment of these precursors with LiAlH4 in
THF followed by quenching the reaction mixture with
degassed water affords, after work-up, the trihydrides
Cp(R3P)RuH3 (1a–d) in good yields.
Ru(1)–H(2) 1.54(3), Ru(1)–H(3) 1.55(3), P(1)–C(15) 1.8410(15), P(1)–C(9)
1.8426(16), P(1)–C(6) 1.8659(16), and P(1)–Ru(1)–H(1) 74.7(10), P(1)–
Ru(1)–H(2) 96.5(10), P(1)–Ru(1)–H(3) 77.6(10), H(1)–Ru(1)–H(2)
64.4(14), H(1)–Ru(1)–H(3) 114.7(16), H(2)–Ru(1)–H(3) 61.7(14).
hydrides forming an equatorial plane in a pseudo-TBP
structure [14]. In fact, the experimental geometry of 1b is
similar to that one of the analogous complex
Cp*(Ph3P)RuH3, which can be better described as a four-
leg piano-stool [15a]. The CNT-Ru and Ru–P vectors,
where CNT is the centroid of the Cp-ring, form an angle
of 125.7ꢁ. Surprisingly enough, although less steric interac-
tion of phosphine with the ring could have been antici-
The new trihydrides 1b–d and the previously reported
complex Cp(Ph3P)RuH3 (1a) were characterized by NMR
and IR spectroscopy, and by X-ray structure of the com-
pound 1b. Like in their Cp* analogues, at room temperature
the hydrides in 1a–d give rise to one, averaged hydride sig-
nal in the region between ꢀ10.3 and ꢀ11.3 ppm coupled
with the phosphine. The IR spectra show corresponding
˚
pated, the Ru-CNT distance of 1.927 A in 1b is slightly
longer than the corresponding parameter in the more
crowded complex Cp*(Ph3P)RuH3 (1.91 A) [22]. By way
˚
˚
of contrast, the Ru–P bond lengths of 2.2465(4) A in 1b
is shorter than the Ru–P distance in Cp*(Ph3P)RuH3
˚
(2.252(1) A), probably due to a combination of a better
Ru–H bands in the region 2010–2001 cmꢀ1
.
donating phosphine and a less bulky Cp ring. These obser-
vations can be explained in terms of interplay of bonding
capabilities of a more donating phosphine and a less donat-
ing cyclopentadienyl ring in 1b in comparison with
Cp*(Ph3P)RuH3. The Ru–H hydride bond lengths,
although subject to the well known uncertainty of finding
The molecular structure of complex 1b is shown in
Fig. 1. Spectroscopic data for the related compound
Cp(Ph3P)RuH3 (1a) have been previously rationalized in
terms of a classical C3v structure, with the bulky phosphine
occupying a position trans to the Cp ring and the three
+
+
PR3
1) LiAlH4 in THF
Ru
Ru
Ru
H
H
NCCH
NCCH
3
3
2) H2O
R P
3
R P
3
CH CN
3
NCCH
NCCH
H
3
3
PF
PF
6
6
Scheme 1. Preparation of [Cp(R3P)Ru(NCCH3)2][PF6] and Cp(R3P)RuH3.

A.L. Osipov et al. / Journal of Organometallic Chemistry 692 (2007) 5081–5085
5083
hydride ligands by X-ray diffraction, fall in a narrow range
of 1.503–1.548 A, which is typical for Ru–H bonds.
4.47 (s, 5, C5H5), 2.56 (m, 2, P(CH(CH3)2)2), 2.41 (s, 6,
CH3CN), 1.08 (dd, J(H–H) = 7.1 Hz, J(P–H) = 14.0 Hz,
6, P(CH(CH3) (CH3))2), 1.05 (dd, J(H–H) = 7.1 Hz,
J(P–H) = 15.1 Hz, 6, P(CH(CH3)(CH3))2). 31P NMR
˚
In summary, we describe
a convenient general
approach to the trihydride complexes Cp(R3P)RuH3 and
the X-ray structure of the complex Cp(Ph2PriP)RuH3.
We are currently exploring application of these com-
pounds to the synthesis of silylhydride derivatives of
ruthenium.
(CDCl3):
d d 133.2 (d,
54.0. 13C NMR (CDCl3):
J(P–C) = 9.1 Hz, Ph2,6), 132.5 (d, J(P–C) = 33.2 Hz, Ph1),
128.5 (CN), 128.2 (d, J(P–C) = 8.8 Hz, Ph3,5), 75.4 (Cp),
27.5 (d, J(P–C) = 22.0 Hz, P(CH(CH3)2)2), 18.9 (s, 2C,
P(CH (CaH3)2)2), 18.6 (s, P(CH(CbH3)2)2), 4.3 (s, CH3CN).
3. Experimental
Elemental analysis for ½CpðPri2PhPÞRuðNCCH3Þ ꢁ½PF6ꢁ,
2
C21H30F6N2P2Ru (587.484). Anal. Calc.: C, 42.93; N, 4.77;
H, 5.15. Found: C, 42.87; N, 4.53; H, 5.36%.
All manipulations were carried out using conventional
high-vacuum or argon-line Schlenk techniques. Solvents
were dried over sodium or sodium benzophenone ketyl
and either kept under argon or distilled into the reaction
vessel by high vacuum gas phase transfer. NMR spectra
3.3. [Cp(PriPh2P)Ru(NCCH3)2][BF4]
Prepared analogously to ½CpðPri3PÞRuðNCCH3Þ2ꢁ½BF4ꢁ,
using PPriPh2 (0.290 g, 1.27 mmol) and [CpRu(NCCH3)3]
[BF4] (0.480 g, 1.27 mmol). Yield: 0.670 g (93%). The corre-
sponding PF6 salt was prepared with a similar yield. IR
were recorded on
a
Bruker (1H, 300 MHz; 13C,
75.4 MHz) and Varian (1H, 400 MHz; 13C, 100.6 MHz;
31P, 161.9 MHz) spectrometers. IR spectra were obtained
as Nujol mulls with an ATI Mattson FTIR spectrometer
1
(Nujol): m(CN) = 2276 cmꢀ1. H NMR (CDCl3): d 7.47–
*
spectrometer. RuCl3 aq was purchased from Precious-
7.37(m, 10, Ph), 4.27 (s, 5, C5H5), 2.76 (m, 1, P(CH(CH3)2)),
2.34 (s, 6, CH3CN) 1.10 (dd, J(H–H) = 7.1 Hz,
J(P–H) = 15.5 Hz, 6, P(CH(CH)3)). 31P NMR (CDCl3): d
51.3. 13C NMR (CDCl3): d 133.9 (d, J(P–C) = 38.4 Hz,
i-Ph), 133.0 (d, J(P–C) = 9.9 Hz, o-Ph), 129.9 (d, J(P–C)
= 2.2 Hz, p-Ph), 128.3 (d, J(P–C) = 9.0 Hz, m-Ph), 128.1
(CH3CN), 76.2 (s, Cp), 29.1 (d, J(P–C) = 24.2 Hz,
P(CH(CH3)2)), 18.8 (s, P(CH(CH3)2)), 4.2 (s, CH3CN). Ele-
mental analysis for [Cp(PriPh2P)Ru(NCCH3)2][PF6],
C24H28F6N2P2Ru (621.501). Anal. Calc.: C, 46.83; N, 4.51;
H, 4.54. Found: C, 46.77; N, 4.87; H, 4.74%.
Metals-on-Line, other reagents were from Sigma-Aldrich.
Complexes [CpRu(NCCH3)3][X] (X = PF6, BF4) [19] and
phosphines were prepared according to the literature
methods.
3.1. General procedure for the preparation of [Cp(R3P)Ru
(NCCH3)2][BF4]: example of [CpðPri3PÞRuðNCCH3Þ ]
2
[BF 4] [23]
Solution of PPri3 (0.161 g, 1.01 mmol) in CH3CN (20 mL)
was added dropwise to a solution of [CpRu(NCCH3)3][BF4]
(0.380 g, 1.01 mmol) in CH3CN (20 mL). The mixture was
stirred for 3 h at ambient temperature. Concentration of
the resulting yellow solution to 5 mL in vacuum and
addition of 40 mL of diethyl ether precipitated the product
in the form of yellow crystals. Yield: 0.470 g (94%). The cor-
responding PF6 salt was prepared with a similar yield. IR
3.4. [Cp(Ph3P)Ru(NCCH3)2][BF4] [21]
This complex was prepared analogously to ½CpðPri3PÞRu
ðNCCH3Þ2ꢁ½BF4ꢁ, using PPh3 (0.348 g, 1.35 mmol) and
[CpRu(NCCH3)3][BF4] (0.500 g, 1.33 mmol). Yield:
0.750 g (94%). Characterization data agree with those
reported in the literature.
(Nujol): m(CN) = 2276 cmꢀ1 1H NMR (CDCl3): d 4.50
.
(s, 5, C5H5), 2.39 (s, 6, CH3CN), 2.29 (d sept, J(H–
H) = 7.2 Hz, J(P–H) = 8.5 Hz, 2, P(CH(CH3)2)2), 1.18
(dd, J(H–H) = 7.2 Hz, J(P–H) = 13.2 Hz, 6, P(CH(CH3)2)).
31P NMR (CDCl3): d 56.0. 13C NMR (CDCl3): d 128.1
(CH3CN), 74.9 (Cp), 26.6 (d, J(P–C) = 18.7 Hz, P(CH
(CH3)2)2), 19.7 (s, P(CH(CH3)2)), 4.0 (s, CH3CN). Elemen-
tal analysis for ½CpðPri3PÞRuðNCCH3Þ2ꢁ½PF6ꢁ, C18H32F6
N2P2Ru (553.468). Anal. Calc.: C, 39.06; N, 5.06; H, 5.83.
Found: C, 38.84; N, 5.08; H, 5.79%.
3.5. [CpðPri3PÞRuH3]
LiAlH4 (0.090 mg, 2.4 mmol), recrystallized from
diethyl ether, was added to a solution of ½CpðPri3PÞRu
ðNCCH3Þ2ꢁ½BF4ꢁ (0.470 g, 0.95 mmol) in 40 ml of THF.
The resulting solution was stirred overnight at ambient tem-
perature and then slowly hydrolyzed with degassed water.
After evaporation of the solvent, the brown residue was
extracted with hexane (3 · 10 ml). Removal of volatiles
and recrystallization at ꢀ30 ꢁC from ether/ethanol (2:1)
afforded 0.200 g of CpðPr3i PÞRuH3 in the form of grey crys-
tals, which deliquesce when brought to room temperature.
3.2. [CpðPri2PhPÞRuðNCCH3Þ ][BF 4]
2
This compound was prepared analogously to ½CpðPri3PÞ
RuðNCCH3Þ2ꢁ½BF4ꢁ, using PPri2Ph (0.232 g, 1.19 mmol)
and [CpRu(NCCH3)3][BF4] (0.450 g, 1.19 mmol). Yield:
0.600 g (95%). The corresponding PF6 salt was prepared with
Yield: 63%. IR (Nujol): m(Ru–H) = 2010 cmꢀ1. H NMR
1
(toluene-d8):
d
4.94 (s, 5, C5H5), 1.42 (d sept,
J(H–H) = 7.0, J(P–H) = 9.2 Hz, 3, P(CH(CH3)2)3), 0.95
(dd, J(H–H) = 7.0 Hz, J(P–H) = 13.6 Hz, 9, PCH(CH)3),
ꢀ11.26 (d, J(P–H) = 20.5 Hz, 3, RuH3). 31P (toluene-d8):
1
a similar yield. IR (Nujol): m(CN) = 2276 cmꢀ1. H NMR
(CDCl3): d 7.55 (m, 2, o-Ph), 7.42 (m, 3, m-Ph and p-Ph),

5084
A.L. Osipov et al. / Journal of Organometallic Chemistry 692 (2007) 5081–5085
d 103.0. 13C (toluene-d8): d 81.5 (s, C5H5), 30.1 (d,
7J(P–C) = 30.2 Hz, PCH(CH3)2), 28.9 (d, J(P–C) =
25.6 Hz, PCH(CH3)2). Elemental analysis for C14H29RuP
(329.42). Anal. Calc.: C, 51.04; H, 8.87. Found: C, 51.10;
H, 8.95%.
Table 1
Crystal data and structure refinement for 1b
Empirical formula
Formula weight
Temperature
C20H25PRu
397.44
123(2) K
˚
Wavelength
0.71073 A
Monoclinic
P2(1)/c
Crystal system
Space group
Unit cell dimensions
3.6. [CpðPri2PhPÞRuH3]
˚
This complex was prepared analogously to CpðPri3PÞ
RuH3 with LiAlH4 (0.100 g, 2.6 mmol) and ½CpðPri2PhPÞ
RuðNCCH3Þ2ꢁ½BF4ꢁ (0.550 g, 1.03 mmol). Yield: 0.320 g
a (A)
11.7325(2)
7.4373(2)
20.1921(4)
90
97.3950(10)
90
1747.27(7)
4
˚
b (A)
˚
c (A)
a (ꢁ)
b (ꢁ)
c (ꢁ)
(85%). IR (Nujol): 2009 cmꢀ1 1H NMR (CD2Cl2): 7.79
.
(m, 2, o-Ph), 7.36 (m, 3, m-Ph and p-Ph), 5.08 (s, 5, Cp),
2.13 (dsept, J(H–H) = 6.8 Hz, J(P–H) = 9.5 Hz, 2 P(CH
(CH3)2)2), 1.00 (dd, J(P–H) = 15.9 Hz, J(H–H) = 6.6
Hz, 6, P(CH(CaH3)2)2), 0.76 (dd, J(P–H) = 15.0
Hz, J(H–H) = 6.9 Hz, 6, P(CH(CbH3)2)2), ꢀ11.33 (d,
J(P–H) = 20.1 Hz, 3, RuH3). 31P NMR (CD2Cl2): 97.6 (s).
13C NMR (CD2Cl2): 134.1 (d, J(P–C) = 9.6 Hz, o-Ph),
129.5 (d, J(P–C) = 2.3 Hz, p-Ph), 127.6 (d, J(P–C) = 8.4 Hz,
m-Ph), 82.0 (d, J(P–C) = 1.7 Hz, Cp), 26.5 (d, J(P–
C) = 31.7 Hz, P(CH(CH3)2)2), 19.5 (d, J(P–C) = 3.5 Hz,
P(CH(CaH3)2)2), 18.8 (s, P(CH(CbH3)2)2). Elemental analysis
for C17H27RuP (363.440). Anal. Calc.: C, 56.18; H, 7.49.
Found: C, 56.47; H, 7.88%.
3
˚
Volume ( A )
Z
Dcalc (Mg/m3)
1.511
0.983
816
Absorption coefficient (mmꢀ1
F(000)
)
Crystal size (mm3)
0.32 · 0.23 · 0.12
1.75–30.01
ꢀ15 6 h 6 16, ꢀ9 6 k 6 10,
ꢀ21 6 l 6 28
11968
5040 [0.0170]
98.5%
0.8911 and 0.7437
h Range for data collection (ꢁ)
Index ranges
Reflections collected
Independent reflections [Rint
Completeness to theta = 30.01ꢁ
Maximum and minimum
transmission
]
Refinement method
Full-matrix least-squares on F2
5040/0/299
Data/restraints/parameters
Goodness-of-fit on F2
Final R indices [I > 2r(I)]
R indices (all data)
3.7. [Cp(PriPh2P)RuH3]
1.065
R1 = 0.0236, wR2 = 0.0587
R1 = 0.0278, wR2 = 0.0612
This complex was prepared analogously to
CpðPri3PÞRuH3 with LiAlH4 (0.101 mg, 2.7 mmol) and
[Cp(PriPh2P)Ru(NCCH3)2][BF4] (0.600 g, 1.06 mmol).
Yield: 0.350 g (83%). IR (Nujol): 2001 cmꢀ1.1H NMR
(C6D6): 7.65 (dt, J(H–H) = 6.9 Hz, 4, o-Ph), 7.03 (m, 6,
m-Ph + p-Ph), 4.88 (s, 5, Cp), 2.25 (m, 1, CH), 0.92 (dd,
J(H–H) = 6.6 Hz, J(P–H) = 16.8 Hz, 6, Me), ꢀ10.30
(d, J(P–H) = 20.1 Hz, 3 H). 31P NMR (C6D6): 87.0 (s).
13C NMR (C6D6): d 133.0 (d, 2J = 10.5 Hz, o-Ph),
128.1–127.5 (m, p,m-Ph), 82.7 (s, C5H5), 29.1 (d,
1J = 33.2 Hz, P(CH(CH3)2)), 18.8 (P(CH(CH3)2)). Elemen-
tal analysis for C20H25RuP (397.456). Anal. Calc.: C, 60.44;
H, 6.34. Found: C, 61.34; H, 6.94%.
Largest difference in peak and hole 0.788 and ꢀ0.597
ꢀ3
˚
(e A
)
given in Table 1. The structure factor amplitudes for all
independent reflections were obtained after the Lorentz
and polarization corrections. A multi-scan absorption cor-
rection was applied. The structures were solved by heavy-
atom methods [24] and refined by full-matrix least squares
2
procedures, using xðjF o2j ꢀ jF 2cjÞ as the refined function.
All hydrogen atoms were found from the difference map.
In the final cycles of refinement, all the non-hydrogen
atoms were refined with anisotropic temperature parame-
ters. The hydride ligands were refined isotropically, other
hydrogen atoms were refined using the riding scheme.
The largest residuals in the final difference Fourier maps
3.8. [Cp(Ph3P)RuH3]
This known complex [14] was prepared analogously to
CpðPri3PÞRuH3, using LiAlH4 (0.088 g, 2,3 mmol) and
[Cp(Ph3P)Ru(NCCH3)2]BF4 (0.550 g, 0.92 mmol). Yield:
0.246 g (62%).
were small (0.788 and ꢀ0.597 e Aꢀ3), location and magni-
˚
tude of the residual electron density was of no chemical
significance.
3.9. Crystal structure determinations of 1b
Acknowledgements
Colourless crystals of 1b were grown from hexane by
cooling the solutions to ꢀ25 to ꢀ30 ꢁC. Single crystal of
1b was coated by polyperfluoro oil and mounted directly
to the Bruker Smart three-circle diffractometer with CCD
area detector at 123(2) K. The crystallographic data and
characteristics of structure solution and refinement are
GIN thanks NSERC for financial support and CFI for a
generous equipment grant. L.G.K. and J.A.K.H. thank the
Royal Society (London) for a Joint Research Grant.
L.G.K. also thanks the Royal Society of Chemistry (Lon-
don) for the RSC Journal Award for International
Authors.

A.L. Osipov et al. / Journal of Organometallic Chemistry 692 (2007) 5081–5085
5085
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Appendix A. Supplementary material
CCDC 647983 contains the supplementary crystallo-
graphic data for this paper. These data can be obtained free
of charge via http://www.ccdc.cam.ac.uk/conts/retriev-
ing.html, or from the Cambridge Crystallographic Data
Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax:
(+44) 1223-336-033; or e-mail: deposit@ccdc.cam.ac.uk.
Supplementary data associated with this article can be
found, in the online version, at doi:10.1016/j.jorganchem.
2007.07.024.
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