9-BBN activation. Synthesis, crystal structure and theoretical characterization of the ruthenium complex Ru[(μ-H)2 BC8H14]2(PCy3)

Article abstract of DOI:10.1016/S0022-328X(03)00343-7

Reaction of the bis(dihydrogen) ruthenium complex RuH₂ (H₂)₂(PCy₃)₂ (1) with an excess of 9-borabicyclononane yields Ru[(μ-H)₂ BC₈H₁₄]₂(PCy₃) (6) and the phosphine adduct PCy₃·HBC₈H₁₄. The new complex is characterized by NMR spectroscopy and X-ray diffraction. New X-ray data on 9-BBN dimer, from a measurement at 180 K, are also reported. DFT calculations (B3LYP) on Ru[(μ-H)₂ BC₈H₁₄]₂(PMe₃) (7), the PMe₃ analogue of 6, confirm the ruthenium (II) formulation with two dihydroborate ligands. The data obtained using PH₃ or PMe₃ as models for PCy₃ in PR₃ ·HBC₈H₁₄ are also discussed.

Full text of DOI:10.1016/S0022-328X(03)00343-7

Journal of Organometallic Chemistry 680 (2003) 182ꢀ187
/
www.elsevier.com/locate/jorganchem
9-BBN activation. Synthesis, crystal structure and theoretical
characterization of the ruthenium complex Ru[(m-H)2BC8H14]2(PCy3)
Khaled Essalah a,1, Jean-Claude Barthelat a, Virginia Montiel b, Se´bastien Lachaize b,
Bruno Donnadieu b, Bruno Chaudret b, Sylviane Sabo-Etienne b,*
a Laboratoire de Physique Quantique, IRSAMC (UMR 5626), Universite´ Paul Sabatier, 118 route de Narbonne, 31062 Toulouse Cedex 4, France
b Laboratoire de Chimie de Coordination du CNRS, 205 route de Narbonne, 31077 Toulouse Cedex 4, France
Received 21 March 2003; received in revised form 23 April 2003; accepted 23 April 2003
Abstract
Reaction of the bis(dihydrogen) ruthenium complex RuH2(H2)2(PCy3)2 (1) with an excess of 9-borabicyclononane yields Ru[(m-
H)2BC8H14]2(PCy3) (6) and the phosphine adduct PCy3×/HBC8H14. The new complex is characterized by NMR spectroscopy and X-
ray diffraction. New X-ray data on 9-BBN dimer, from a measurement at 180 K, are also reported. DFT calculations (B3LYP) on
Ru[(m-H)2BC8H14]2(PMe3) (7), the PMe3 analogue of 6, confirm the ruthenium (II) formulation with two dihydroborate ligands.
The data obtained using PH3 or PMe3 as models for PCy3 in PR3×/HBC8H14 are also discussed.
# 2003 Elsevier Science B.V. All rights reserved.
Keywords: Boranes; Ruthenium; Polyhydrides; DFT; 9-BBN
1. Introduction
of the boron reagent. In particular, we have recently
shown that s-complexes can be stabilized by using the
tricoordinated neutral pinacolborane compound [9].
The complex RuH[(m-H)2Bpin](s-HBpin)(PCy3)2 (2)
Borane activation by transition metal complexes
continues to attract considerable attention, not only
because of the catalytic potential but also because of the
versatile structures and bonding modes associated to
this chemistry. The last decade has shown considerable
achievement on the characterization of boryl and s-
borane complexes and on the involvement of these
species in several catalytic processes such as hydrobora-
tion or diboration of unsaturated substrates, and
(HBpinꢁHBO2C2Me4) can thus be synthesized by
/
adding an excess of HBpin to 1. The two boron ligands
are attached to the ruthenium center by two different
coordination modes: s-coordination and dihydroborate
ligation. When using only one equivalent HBpin, the
complex RuH2(s-H2)(s-HBpin)(PCy3)2 (3) can be gen-
erated. X-ray data and theoretical calculations demon-
strate that 3 is stabilized by two s-ligands, a borane and
a dihydrogen [10]. In the case of 9-borabicyclononane
functionalization of alkanes and arenes [1ꢀ7].
/
Our group is currently involved in investigations
based on the activation of boranes by the ruthenium
bis(dihydrogen) precursor RuH2(H2)2(PCy3)2 (1) [8].
Our first results show that the nature of the final
product is highly dependent on the experimental condi-
tions (stoichiometric ratio, solvent. . .) and on the nature
(9-BBN dimerꢁ(HBC8H14)2) activation, we reported
/
some years ago that addition of one equivalent of 9-
BBN to a suspension of 1 in hexane led to the formation
of
a
dihydroborate compound RuH[(m-H)2B-
C8H14](PCy3)2 (4) characterized by NMR data as a 16
electron complex [11]. Dihydrogen bubbling led to
borane elimination and regeneration of the starting
complex 1 via the dihydrogen intermediate RuH[(m-
H)2 BC8H14](H2)(PCy3)2 (5).
* Corresponding author. Tel.: ꢂ
553003.
E-mail address: sabo@lcc-toulouse.fr (S. Sabo-Etienne).
/
33-5-61-333177; fax: ꢂ33-5-61-
/
We now describe the synthesis and characterization of
a new ruthenium complex Ru[(m-H)2BC8H14]2(PCy3) (6)
resulting also from the activation of 9-borabicyclono-
1
Permanent address: Unite´ de Recherche de Physico-Chimie
Mole´culaire, Institut Pre´paratoire des Etudes Scientifiques et
Techniques (IPEST), Boite Postale 51, 2070 La Marsa, Tunisia.
0022-328X/03/$ - see front matter # 2003 Elsevier Science B.V. All rights reserved.
doi:10.1016/S0022-328X(03)00343-7

K. Essalah et al. / Journal of Organometallic Chemistry 680 (2003) 182ꢀ
/
187
183
nane. X-ray data and theoretical calculations support
the formulation of a bis(dihydroborate) complex.
2. Results and discussion
Addition of an excess of 9-BBN dimer to a toluene
suspension of RuH2(H2)2(PCy3)2 (1) results in gas
evolution and formation of an orange solution. Cooling
at ꢃ35 8C affords an orange solid analyzed as Ru[(m-
/
H)2BC8H14]2(PCy3) (6) (see Scheme 1) and characterized
by NMR and X-ray diffraction. The 1H-NMR spectrum
of 6 shows one broad high field resonance at room
temperature at d ꢃ12.34 resolved as a doublet between
/
263 and 233 K indicative of a coupling with only one
phosphine with a JHꢀP constant of 9 Hz. The relaxation
time T1 of the hydrides has been determined as 95 ms at
243 K and 300 MHz in agreement with the absence of
any dihydrogen ligand. The presence of four hydrides is
confirmed by the observation of a quintet at d 104.9
Fig. 1. ORTEP drawing of complex Ru[(m-H)2BC8H14]2(PCy3) (6).
Table 1
Crystal data for Ru[(m-H)2BC8H14]2(PCy3) (6)
(JHꢀP
ꢁ
9 Hz) on the 31P-NMR spectrum recorded with
/
selective decoupling of the protons of the PCy3 ligand.
The 11B-NMR spectrum of 6 shows one broad reso-
nance at room temperature at d 58.8. Similar chemical
shifts were reported for dihydroborate niobocene com-
plexes [12,13].
The X-ray structure determined at 160 K is depicted
in Fig. 1. Crystal data are reported in Table 1 and
selected bond distances and angles are listed in Table 2
together with DFT results for comparison (see below).
The ruthenium is surrounded by one phosphine and two
Chemical formula
Formula weight
Crystal system
Space group
C34H65B2PRu
627.52
triclinic
¯
P1
/
Z, calculated density (Mg mꢃ3
)
2, 1.273
0.549
676
Absorption coefficient (mmꢃ1
F(0 0 0)
)
˚
a (A)
10.4997(12)
11.0584(12)
15.6545(18)
77.927(13)
80.427(13)
67.742(12)
1637.4(3)
160(2)
˚
b (A)
˚
c (A)
a (8)
b (8)
g (8)
dihydroborate ligands with a B1ꢀ
/
Ruꢀ
/
B2 angle of
˚
P distance is 2.2150(5) A. As a
147.68(8)8. The Ruꢀ
/
˚
V (A)
Temperature (K)
result of a vacancy trans to the phosphine, this value is
shorter than what is normally found for other ruthe-
Data/restraints/parameters
Goodness of fit on F2
5959/0/359
1.041
˚
nium complexes with PCy3 ligand (ca. 2.35 A) [8,9,14].
The two PꢀRuꢀB angles are slightly different and equal
to 103.89(6) and 108.37(6)8. The RuꢀB1 distance is
R1[I ꢀ/2s(I)]
0.0233
0.0570
/
/
wR2
˚
Largest difference peak and hole (e A
/
ꢃ3
)
0.405 and ꢃ0.451
/
˚
˚
B2 distance is 2.085(2) A,
2.160(2) A, whereas the Ruꢀ
/
thus slightly shorter. Analysis of the distances involving
the hydrogen atoms bound to the ruthenium should be
considered cautiously. Four hydrogen atoms were how-
ever located in the vicinity of the ruthenium with Ruꢀ
/
H
˚
distances of 1.63 A (av). The ruthenium and the four
hydrogen atoms H(1a), H(1b), H(2a) and H(2b) are
coplanar. The distances between the two borons and the
˚
hydrogens are in the range 1.35(2) and 1.41(2) A. These
values are close to those found in niobium metal
complexes coordinating the 9-BBN ligand in a similar
fashion. The BꢀH distances in Cp2Nb[(m-H)2BC8H14]
/
˚
are 1.38(7) and 1.39(6) A [12], whereas slightly different
values were obtained for the substituted SiMe3C5H4
Scheme 1.

184
K. Essalah et al. / Journal of Organometallic Chemistry 680 (2003) 182ꢀ187
/
Table 2
X-ray data for Ru[(m-H)2BC8H14]2(PCy3) (6) and selected B3LYP-
optimized geometrical parameters for Ru[(m-H)2BC8H14]2(PMe3) (7)
obtained from an NBO analysis reflect an important
delocalisation between the ruthenium, the two borons
and the four bridging hydrogens, as seen for example
from the following values: W(Ruꢀ
0.387, W(RuꢀH1a) 0.274, W(Ruꢀ
H1a) 0.578, W(B2ꢀH1b) 0.565. A more detailed NBO
analysis does not seem to be appropriate, as it was
impossible to obtain a Lewis structure representative of
the coordination mode of two dihydroborate ligands on
the same ruthenium atom.
/
B1) 0.361, W(Ruꢀ
/
B2)
6, RX
7, DFT
/
/
H1b) 0.282, W(B1ꢀ
/
Ruꢀ
Ruꢀ
Ruꢀ
Ruꢀ
Ruꢀ
Ruꢀ
Ruꢀ
B(1)ꢀ
B(1)ꢀ
B(2)ꢀ
B(2)ꢀ
/
B(1)
2.160(2)
2.085(2)
2.2150(5)
1.63(2)
1.66(2)
1.60(2)
1.63(2)
1.35(2)
1.37(2)
1.40(2)
1.41(2)
2.179
2.122
2.230
1.726
1.726
1.726
1.726
1.404
1.404
1.414
1.414
/
/B(2)
/P
/
H(1a)
H(2a)
H(1b)
H(2b)
/
/
Analysis of the crude 1H- and 31P-NMR spectra of the
solution obtained after mixing 1 and 9-BBN dimer in
toluene-d8 shows apart from the formation of 6, the
presence of new signals attributed to the phosphine
/
/
H(1a)
H(2a)
H(1b)
H(2b)
/
/
/
adduct PCy3×
11B ꢃ
14.7, 128.38 MHz;) (see Scheme 1) and less than
5% of RuH[(m-H)2 BC8H14](H2)(PCy3)2 (5) (293 K, d
1H, ꢃ9.3 (vbr) 300 MHz, d 31P, 66.0 (br) 121.49 MHz,
[11]).
/
HBC8H14 (293 K: d 31P 10.2, 121.49 MHz;
B(2)ꢀ
B(1)ꢀ
B(2)ꢀ
PꢀRuꢀ
PꢀRuꢀ
PꢀRuꢀ
PꢀRuꢀ
H(1b)ꢀ
H(1a)ꢀ
H(1a)ꢀ
H(1b)ꢀ
/
Ruꢀ
Ruꢀ
Ruꢀ
/
B(1)
P
147.68
150.2
101.5
108.3
91.0
d
/
/
/
103.89(6)
108.37(6)
94.0(8)
/
/
P
/
/
H(1a)
H(2a)
H(1b)
H(2b)
/
/
/
90.1(8)
91.0
/
/
90.2(8)
91.0
The phosphine adduct was also characterized theore-
tically. We have optimized the 9-BBN dimer and the two
/
/
90.5(8)
91.0
/
Ruꢀ
/
H(2b)
H(2a)
77.8(11)
75.3(11)
94.9(17
92.7(13)
77.0
77.9
/
Ruꢀ
B(1)ꢀ
/
adducts PR3×
/
HBC8H14 (RꢁH, Me) at the DFT/
/
/
/
H(2a)
H(2b)
101.2
98.8
B3LYP level. The corresponding geometries are de-
picted in Fig. 2 and optimized values of selected
geometrical parameters as well as X-ray data for the 9-
BBN dimer are reported in Table 3. The X-ray structure
of 9-BBN was previously reported in 1973 [16], but we
have now obtained new data at low temperature for
better location of hydrogen atoms. The good agreement
between the X-ray and the B3LYP-optimized geometries
of the dimer testifies of the ability of the B3LYP hybrid
functional to correctly describe two-electron three-
center bonds. Moreover, an interesting comparison
can be made with very recent X-ray and neutron data
/
B(2)ꢀ
/
See Fig. 1 for labeling of the atoms. Distances are in angstrom and
angles in degree.
˚
ligand (1.38(4) and 1.28(3) A) [13]. A ruthenium
complex with a BBN inserted into the RuꢀC bond of
a metalated phosphine was reported with one Bꢀ
/
/
H
˚
distance of 1.367(21) A [15]. In our complex, small
differences observed for the angles and the distances
involving the two borons could indicate a disymmetry.
An alternative formulation to the most plausible bis(di-
hydroborate) structure could be an intermediate struc-
ture with only one dihydroborate ligand, a hydrido and
a s-borane ligand. Such an hypothesis however seems
unlikely and is not in agreement with NMR data
showing at all temperatures only one signal for the
four equivalents hydrogen.
DFT/B3LYP studies also favor the formation of the
bis(dihydroborate) species. The model complex Ru[(m-
H)2BC8H14]2(PMe3) (7) has been characterized on the
singlet potential energy surface and has been shown to
be a local minimum by vibrational frequency calcula-
tions. Optimized geometrical parameters and X-ray data
are compared in Table 2. Our calculation confirms the
overall structure found by X-ray diffraction. It is
interesting to note that the difference observed for the
reported by Marder on the analogous dimesitylborane
˚
H distance of 1.280(15) A
dimer (HBMes)2 [17]. A Bꢀ
/
was determined by X-ray diffraction, whereas single
crystal neutron diffraction at 20 K led to a value of
˚
1.340(2) A. In our case, the 9-BBN dimer is character-
˚
H distance of 1.28(2) A, as determined by
X-ray, whereas the DFT/B3LYP calculation gives a
ized by a Bꢀ
/
˚
value of 1.341 A. This latter value thus correlates
perfectly with the neutron determination on the dime-
sityl borane dimer. This comparison emphasises the
importance of DFT calculations for a better estimation
of the parameters concerning hydrogen atoms.
The decrease of the Bꢀ
/
P bond length in the PMe3×
/
HBC8H14 adduct compared to PH3×
/
HBC8H14 is in
agreement with the basicity of the PMe3 ligand. The
formation of the phosphine adduct corresponds to the
following equation:
Pꢀ
DFT calculations. A comparison of the Bꢀ
in 7 with free 9-BBN dimer (see below) allows an
estimation of the degree of activation of the BꢀH bond
during the coordination process. The lengthening is
about 5% from the free ligand to 7 by DFT, and ca. 5ꢀ
10% from the free ligand to 6 by X-ray. Wiberg indices
/
Ruꢀ
/
B angles in the X-ray data is well reproduced by
/
H distances
(HBC8H14)2 ꢂ2PR30 2PR3×HBC8H14
(1)
/
The calculated DE energy difference associated with
/
this equation is 12.3 kcal molꢃ1 in the case of PH3
whereas a negative value of ꢃ
11.1 kcal molꢃ1 is
/

K. Essalah et al. / Journal of Organometallic Chemistry 680 (2003) 182ꢀ
/
187
185
Fig. 2. The B3LYP-optimized structures of 9-BBN×
/
([HBC8H14]2) and the phosphine adducts PH3×
/
HBC8H14 and PMe3×HBC8H14.
/
entropic factor leads to DG8 values of 21.4 and 0.1 kcal
molꢃ1, respectively. These values indicate that the
formation of the phosphine adduct cannot occur with
PH3 whereas it is likely with PMe3, in better agreement
with the experimental observation. This demonstrates
that PH3 cannot be used as a reasonable model of PCy3
in our calculations.
Table 3
X-ray data for 9-BBN and selected B3LYP-optimized geometrical
parameters for 9-BBN and the phosphine adducts PH3×
PMe3×
/HBC8H14 and
/
HBC8H14
9-BBN RX 9-BBN
DFT
PH3×
HBC8H14
DFT
/
PMe3×
HBC8H14
DFT
/
Bꢀ
/
H (av)
1.27(2)
1.579(2)
1.804(3)
1.341
1.598
1.822
1.232
1.625
1.240
1.634
Bꢀ
/
C (av)
B1ꢀ
B1ꢀ
/B2
ꢀ/
2.040
ꢀ/
1.995
3. Conclusion
/P
ꢀ/
ꢀ/
Hꢀ
(av)
BꢀHꢀ
(av)
CꢀBꢀ
(av)
C1ꢀ
H1ꢀ
PꢀB1ꢀ
/
Bꢀ
/
H
90(1)
94.4
ꢀ
/
ꢀ
/
In summary, we have isolated the first complex in
which two 9-BBN ligands are coordinated to the same
metal with a dihydroborate mode. This complex is
obtained from the bis(dihydrogen) complex 1 in pre-
sence of an excess of 9-BBN, the driving force being the
/
/
B
90(1)
85.6
ꢀ/
ꢀ/
/
/
C
111.6(2)
124.20(6)
111.2
124.4
108.5
107.3
/
B1ꢀ
B1ꢀ
C1
/
B2
ꢀ/
93.4
111.5
ꢀ/
93.3
115.0
formation of the phosphine adduct PCy3×
/HBC8H14.
/
/P
ꢀ/
ꢀ/
ꢀ/
ꢀ/
Our study demonstrates that in the field of borane
activation, it is highly necessary to control the experi-
mental conditions. Stoichiometric ratio and presence of
water traces are in particular very important factors.
We have noted that a full NBO analysis of our system
is not appropriate for such a delocalised electron density
/
/
˚
See Fig. 2 for labeling of the atoms. Distances are in A and angles in
8.
obtained in the case of PMe3. Standard enthalpies (DH8)
and Gibbs free energies (DG8) at 298.15 K were
obtained from vibrational frequency calculations. The
DH8 values for the PH3 and PMe3 adducts are 12.9 and
through four 3 center-2 electron Bꢀ
/
Hꢀ
/
Ru bonds.
Moreover, as a result of possible interaction of the
phosphine with the borane, we have shown that for
borane activation by our ruthenium precursor, it is
necessary for computational investigations to model the
PCy3 ligand by PMe3. It is remarkable that in the case of
ꢃ
10.5 kcal molꢃ1, respectively. They are not very
/
different from the DE values. Taking into account the

186
K. Essalah et al. / Journal of Organometallic Chemistry 680 (2003) 182ꢀ187
/
silane activation by the same precursor, PH3 was a good
model as the nature of the phosphine had little effect on
the properties of the final product [14]. This is not true
for borane activation. This should be probably the same
for any other metal.
RuH(H2)). 31P{1H} NMR (toluene-d8, 121.49 MHz)
293 K: 66.0 (br); 243 K: 65.8 (s).
4.4. Crystal data for 6
Data were collected at low temperature (Tꢁ160 K)
/
on a Stoe Imaging Plate Diffraction System, equipped
with an Oxford Cryosystems Cryostream Cooler Device
4. Experimental
and using a graphite-monochromated Moꢀ
/
Ka radiation
4.1. General
˚
0.71073 A). The final unit cell parameters were
(lꢁ
/
obtained by least-squares refinement of a set of 8000
well measured reflections, and crystal decay was mon-
itored by measuring 200 reflections by image. No
significant fluctuation of the intensities was observed.
A semi-empirical correction absorption was applied [18].
The structure was solved by direct methods using the
program SIR92, [19] and refined by least-squares proce-
dures on F2 with SHELXL-97 [20] and WINGX [21]. The
atomic scattering factors were taken from international
tables for X-ray crystallography [22]. All hydrogen
atoms were located on a difference Fourier map, but
introduced and refined with a riding model. Hydride
atoms were isotropically refined. All non-hydrogen
atoms were anisotropically refined, a weighting scheme
was used in the last cycles of refinement. Weights are
All reactions were performed in an inert atmosphere
glovebox or by using standard Schlenk techniques under
argon. Solvents were dried and distilled according to
standard procedures and degassed prior to use. All
reagents were purchased from Aldrich except RuCl3×
/
3H2O which came from Johnson Matthey Ltd.
RuH2(H2)2(PCy3)2 (1) was prepared according to pub-
lished procedures [8]. All NMR solvents were dried
using appropriate methods and degassed prior to use.
NMR spectra were recorded on Bruker DPX 300 or
1
AMX 400 spectrometers. H-NMR chemical shifts are
reported in ppm relative to residual 1H signals in
toluene-d7 (d 2.13) and 31P-NMR in ppm downfield of
an external 85% solution of phosphoric acid. 11B-NMR
chemical shifts are referenced to a BF3×
/Et2O external
calculated from the following formula: wꢁ
/
1/[s2(F2o)ꢂ
/
standard solution.
(aP)2ꢂ (F2oꢂ2F2c)/3. The molecule was
drawn with the program ORTEP3 [23].
/
bP] where Pꢁ
/
/
4.2. Synthesis and characterization of Ru[(m-
H)2BC8H14]2(PCy3) (6)
4.5. Computational details
Toluene (3 ml) was added in the drybox to
RuH2(H2)2(PCy3)2 (1) (102.4 mg, 0.153 mmol) and 9-
BBN dimer (114.2 mg, 0.468 mmol) in a Schlenk tube.
Dihydrogen evolution was immediately observed fol-
lowed by gradual dissolution of the solids within 2 h,
producing an orange solution. The tube was then kept in
DFT calculations were performed with the GAUSSIAN
98 series of programs [24] using the non-local hybrid
functional denoted as B3LYP [25]. For ruthenium, the
core electrons were represented by a relativistic small-
core pseudopotential using the DurandꢀBarthelat
/
the fridge at ꢃ35 8C. The resulting orange crystals were
/
method [26]. The 16 electrons corresponding to the 4s,
4p, 4d and 5s atomic orbitals were described by a (7s, 6p,
6d) primitive set of Gaussian functions contracted to
(5s, 5p, 3d). Standard pseudopotentials developed in
Toulouse were used to describe the atomic cores of all
other non-hydrogen atoms (C, B and P) [27]. A double
plus polarization valence basis set was employed for
each atom (d-type function exponents were 0.80, 0.60
and 0.45, respectively). For hydrogen, a standard
primitive (4s) basis contracted to (2s) was used. A p-
type polarization function (exponent 0.9) was added for
the hydrogen atoms directly bound to ruthenium. The
geometry of the various critical points on the potential
energy surface was fully optimized with the gradient
method available in GAUSSIAN 98. Calculations of
harmonic vibrational frequencies were performed to
determine the nature of each critical point. See Ref.
[28] for NBO analysis.
filtered off and dried under vacuum (yield 40%). Anal.
Calc. for C34H65B2PRu: C, 65.06; H, 10.46; Found C,
1
65.22; H, 10.39%. H-NMR (toluene-d8, 300.13 MHz)
293 K: d 2ꢀ
/
1.5 (m, 61H, C8H14 and PCy3), ꢃ
/
12.43 (br,
4H, RuꢀH4); 243 K: ꢃ
/
/
12.34 (d, 4H, RuꢀH4, JHꢀP
/
ꢁ9
/
Hz). T1 min (toluene-d8, 300.13 MHz, 243 K) 95 ms.
31P{1H} NMR (toluene-d8, 121.49 MHz) 293 K: 105.6
(s); 243 K: 105.5 (s). 31P{1H(PCy3)} NMR (toluene-d8,
161.98 MHz) 243 K: 104.9 (quintet, JHꢀP
ꢁ9 Hz).
/
11B{1H} NMR (toluene-d8, 96.29 MHz) 293 K: 58.8
(br).
4.3. NMR data for RuH[(m-H)2BC8H14](H2)(PCy3)2
(5)
1H-NMR (toluene-d8, 300.13 MHz) 293 K: d ꢃ
(vbr); 243 K: ꢃ4.9 (br, Ru-m-H2B), ꢃ11.48 (brt,
/
9.3
/
/

K. Essalah et al. / Journal of Organometallic Chemistry 680 (2003) 182ꢀ
/
187
187
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5. Supplementary material
Crystallographic data for the structural analysis have
been deposited with the Cambridge Crystallographic
Data Centre, CCDC no. 206648 and 206649 for 6 and 9-
BBN dimer, respectively. Copies of this information
may be obtained free of charge from The Director,
CCDC, 12 Union Road, Cambridge CB2 1EZ, UK
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Acknowledgements
This work is supported by the CNRS. We thank the
CINES (Montpellier, France) for a generous allocation
of computer time.
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