The clusters HRu3W(η5-Cp)(CO)11-x(PPh3) xBH (x = 1, 2): Preparations, characterizations and the crystal structure of HRu3W(η5-Cp)(CO)10(PPh3)BH

Article abstract of DOI:10.1016/S0022-328X(00)00216-3

The clusters HRu₃W(η⁵-Cp)(CO)_11-x(PPh₃) _xBH (x = 1, 2) have been prepared by reaction of PPh₃ with HRu₃ W(η⁵-Cp)(CO)₁₁BH after Me₃NO-MeCN-activat

Full text of DOI:10.1016/S0022-328X(00)00216-3

www.elsevier.nl/locate/jorganchem
Journal of Organometallic Chemistry 609 (2000) 89–94
The clusters HRu3W(h5-Cp)(CO)11−x(PPh3)xBH (x=1, 2):
preparations, characterizations and the crystal structure of
HRu3W(h5-Cp)(CO)10(PPh3)BH
Catherine E. Housecroft a,*, Dorn M. Nixon b, Arnold L. Rheingold c
a Institut fu¨r Anorganische Chemie, Spitalstrasse 51, Basel CH-4056, Switzerland
b Department of Chemistry, Uni6ersity of Cambridge, Lensfield Road, Cambridge CB2 1EW, UK
c Department of Chemistry, Uni6ersity of Delaware, Newark, DE 19716, USA
Received 19 February 2000; received in revised form 16 April 2000
Abstract
The clusters HRu3W(h5-Cp)(CO)11−x(PPh3)xBH (x=1, 2) have been prepared by reaction of PPh3 with HRu3W(h5-
Cp)(CO)11BH after Me3NOꢀMeCN-activation; HRu3W(h5-Cp)(CO)10(PPh3)BH has also been made by the reaction of
HRu3(CO)8(PPh3)B2H5 with [(h5-Cp)W(CO)3]2. The cluster-bound hydrogen atoms respond to the charge density changes as PPh3
is introduced into HRu3W(h5-Cp)(CO)11BH, and proton chemical shift correlations are presented for this and related systems.
The single crystal structure of HRu3W(h5-Cp)(CO)10(PPh3)BH has been determined. © 2000 Elsevier Science S.A. All rights
reserved.
Keywords: Ruthenium; Boron; Heterometallic cluster; Hydride; Phosphine
tution and by cluster expansion starting with the PPh3
ligand in an Ru3-precursor. We compare the cluster
hydrogen distributions in a series of isoelectronic het-
erometallic clusters in which the heterometal is varied,
and correlate the 1H-NMR spectroscopic chemical
shifts of the cluster-bound hydrogen atoms to substitu-
tion pattern.
1. Introduction
Our interest in homometallic and heterometallic but-
terfly clusters containing an interstitial boron atom has
been wide ranging [1–3] and has included studies of the
reactivity of the boron centre and the use of these
clusters as building blocks to higher nuclearity clusters
in which the boron atom becomes fully interstitial. We
have reported a number of heterometallic butterfly
species containing an Ru3M%B-core in which M%=Mo
[4], W [4], Fe [5], Rh [6], Ir [6]. In particular, we have
pointed to the fact that changing the metal can lead to
a change in the number of cluster-bound hydrogen
atoms (as a response to a change in metal electron
count) and that this, in turn, can provide a means of
controlling the chemistry of the cluster, for example in
the assembly of linked clusters [7]. In this paper, we
look at methods of introducing a PPh3 ligand into
HRu3W(h5-Cp)(CO)11BH, both by PPh3-for-CO substi-
2. Experimental
2.1. General data
FT-NMR spectra were recorded on a Bruker WM
250 spectrometer (1H) or AM 400 spectrometer (31P,
1
1
11B and H); H shifts are reported with respect to l 0
for Me4Si, 11B-NMR with respect to l 0 for F3B·OEt2,
and 31P-NMR with respect to l 0 for 85% H3PO4.
Solution infrared spectra were recorded on a Perkin–
Elmer FT 1710 spectrophotometer, and fast atom bom-
bardment (FAB) mass spectra using Kratos instruments
(3-NBA matrix=3-nitrobenzyl alcohol).
* Corresponding author. Tel.: +41-61-2671004; fax: +41-61-
2671014.
E-mail address: catherine.housecroft@unibas.ch (C.E. Housecroft).
0022-328X/00/$ - see front matter © 2000 Elsevier Science S.A. All rights reserved.
PII: S0022-328X(00)00216-3

90
C.E. Housecroft et al. / Journal of Organometallic Chemistry 609 (2000) 89–94
Reactions were carried out under argon using stan-
a flask containing PPh3 (4 mg, 0.016 mmol). After 90
min stirring, solvent was removed in vacuo. The prod-
ucts were separated by TLC eluting with hexane–
CH2Cl2 (3:1). The first fraction was HRu3W(h5-Cp)-
(CO)11BH (orange, :20%). The main product was
HRu3W(h5-Cp)(CO)10(PPh3)BH (2), (orange, typically
:50%) and the final band was HRu3W(h5-
Cp)(CO)9(PPh3)2BH (3), (:10%). Smaller fractions
were observed on the TLC plate but were not collected.
dard Schlenk techniques; solvents were pre-dried and
distilled under N2. Separation of products was by thin
layer plate chromatography (TLC) using Kieselgel 60-
PF-254 (Merck). Photolysis experiments used a mercury
high-pressure lamp with the sample contained in a
quartz tube flushed with argon. HRu3W(h5-
Cp)(CO)11BH (1) [4] and HRu3(CO)8(PPh3)B2H5 [8]
were prepared as previously reported. Triphenylphos-
phine was used as supplied (Aldrich). Yields are quoted
with respect to starting cluster; yields are often variable
and typical values are quoted. Abbreviations: Cp,
C5H5; Cp*, C5Me5.
1
Compound 2: H-NMR (CDCl3, 298 K) l +7.5–7.4
(m, Ph), +5.21 (s, h5-C5H5), −5.6 (br, RuꢀHꢀB),
−20.4 (d, J(PH) 2.3 Hz, RuꢀHꢀRu); 11B-NMR
(CDCl3, 298 K) l +129; 31P-NMR (CDCl3, 298 K) l
+37.5; IR (hexane, cm−1) w(CO) 2082 w, 2067 m, 2045
vs, 2013 s, 2000 s, 1989 m, 1979 m, 1958 m, 1902 m.
FABMS: 1106 (P+, correct isotope distribution) with
2.2. Photolysis of HRu3W(p5-Cp)(CO)11BH with PPh3
HRu3W(h5-Cp)(CO)11BH (11 mg, 0.013 mmol) and
PPh3 (3 mg, 0.013 mmol) were dissolved in THF (1 ml)
and photolysed for 21 h during which time, the orange
solution darkened. After TLC separation eluting with
hexane–CH2Cl2 (2:1), the following fractions were col-
lected and identified by comparison with their literature
spectroscopic data: H4Ru4(CO)12 (trace amounts) [9],
H4Ru4(CO)11(PPh3) (:10%) [10], unreacted HRu3W-
(h5-Cp)(CO)11BH (:40%) and H3Ru3W(h5-Cp)(CO)11
(:40%) [4].
ten sequential CO losses; calc. for
C
33
1H22 11B
O
10
12
16
31P 101Ru3 184W; 1107.
2.4.1. Compound 3
1H-NMR (CDCl3, 298 K) l +7.6–7.4 (m, Ph),
+5.36 (s, h5-C5H5), −5.6 (br, RuꢀHꢀB), −19.5 (d,
J(PH) 8.5 Hz, RuꢀHꢀRu); 11B-NMR (CDCl3, 298 K) l
+129; IR (hexane, cm−1) w(CO) 2067 w, 2057 m, 2046
m, 2025 m, 2011 s, 1993 m, 1978 m, 1965 m, 1955 w,
1948 w, 1936 w, 1885 m. FABMS: 1342 (P+, correct
isotope distribution) with nine sequential CO losses;
12
2.3. Photolysis of HRu3(CO)8(PPh3)B2H5 with
[(p5-Cp)W(CO)3]2
calc. for
C
1H37 11B 16O9 31P2 101Ru3 184W; 1341.
50
2.5. Crystal structure determination of 2
HRu3(CO)8(PPh3)B2H5 (8 mg, 0.001 mmol) was dis-
solved in THF (0.5 ml) and added to [(h5-Cp)W(CO)3]2
(7 mg, 0.001 mmol). The resulting solution was pho-
tolysed for 8 h. TLC separation, eluting with hexane–
CH2Cl2 (2:1) gave a number of fractions, but only the
three main fractions were collected. The first fraction
was identified as Ru3(CO)12 (:20%); the second band
was H4Ru4(CO)11(PPh3) (:10%) [10]. The third frac-
tion (orange, 510%) was HRu3W(h5-Cp)(CO)10-
(PPh3)BH (2). The low yield meant that only partial
characterization (11B-NMR, IR spectroscopic data and
FABMS) was possible; full data are given in Section
2.4.
A suitable crystal of 2 was grown from a CH2Cl2
solution kept at 0°C for several days. Crystallographic
data are collected in Table 1. All specimens screened
diffracted weakly and broadly indicative of high ther-
mal activity. Systematic absences in the diffraction data
allowed the unique assignment of the orthorhombic
space group shown. The unit-cell dimensions were ob-
tained from the angular settings of 25 reflections (20B
2qB30). Data were collected to a 2qmax=45° yielding
1773 observed reflections. The structure was solved by
direct methods and refined by full-matrix, least-squares
methods. The metal, phosphorus and oxygen atoms
were refined anisotropically. Several of the carbon
atoms became non-positive-definite on attempted an-
isotropic refinement and the effort was abandoned.
Hydrogen atoms were placed in idealized locations. All
software was included in the SHELXTL 5.0 library [11].
2.4. Acti6ation of HRu3W(p5-Cp)(CO)11BH with
Me3NO–MeCN and reaction with PPh3
HRu3W(h5-Cp)(CO)11BH (14 mg, 0.016 mmol) was
dissolved in CH2Cl2 (6 ml) and MeCN (2 ml). The
solution was cooled to −76°C in a dry ice–acetone
bath and a molar equivalent of Me3NO (1.2 mg) dis-
solved in MeCN (5 ml) was added dropwise. The
reaction was monitored by IR spectroscopy (new ab-
sorptions appeared at 2068, 2041, 2011, 1991 and 1952
cm−1) and when no more HRu3W(h5-Cp)(CO)11BH
was evident (after 15 min), the solution was filtered into
3. Results and discussion
The homometallic boride cluster HRu4(CO)12BH2
undergoes phosphine substitution reactions relatively
readily, with the first and second substitution positions
for mondentate ligands such as PPh3 being at remote

C.E. Housecroft et al. / Journal of Organometallic Chemistry 609 (2000) 89–94
91
pied by a W(h5-Cp)(CO)2 unit, and, compared to
HRu4(CO)12BH2 (1) has one fewer cluster hydrogen
atoms.
wingtip Ru atoms and in equatorial sites. For the
disubstituted compound HRu4(CO)10(PPh3)2BH2, two
isomers are formed with substitution patterns (1,10)
and (1,11) using the numbering scheme in Scheme 1
[12]. In the case of the incoming ligand being Ph2PH,
the first site of attack is an equatorial, wingtip Ru site
(e.g. site 1 in Scheme 1), with the second substitution
occurring at an equatorial, hinge Ru atom to give a
mixture of isomers, with substitution patterns (1,6) and
either (1,8) or (1,9) [13]. We initially undertook the
study of phosphine substitution in the heterometallic
compound HRu3W(h5-Cp)(CO)11BH (1), (Scheme 1),
as a comparative investigation with respect to substitu-
tion in HRu4(CO)12BH2. In 1, one wingtip site is occu-
Initial attempts at direct reaction between 1 and PPh3
under ambient conditions (stirring in CH2Cl2 solution
at room temperature (r.t.) for 4 days) were unsuccess-
ful, giving back only starting material. Since these
conditions failed to produce a substituted derivative of
1, we attempted use of photolysis; reaction did occur
after an overnight photolysis. In addition to unreacted
starting cluster, the main products were the non-boron
containing tetrahedral clusters H4Ru4(CO)11(PPh3) and
H3Ru3W(h5-Cp)(CO)11. It seems likely that the latter
compound (which, in solution, exists as two isomers [4])
was formed by boron abstraction by the PPh3 Lewis
base and closure of the Ru3W framework from a
Table 1
Crystallographic data for compound 2
62-electron butterfly to
a 60-electron tetrahedron
(Scheme 2). This result in itself is interesting since
competitive reactions of this nature had not proved a
problem in photolysis reactions of HRu4(CO)12BH2
with PPh3 or other phosphines [12]. The cluster closure
in Scheme 2 requires not only cluster-hydrogen atom
redistribution, but also the gain of a hydrogen atom
during boron abstraction. That the reaction is not
simple is supported by the formation of H4Ru4(CO)11-
(PPh3).
Formula
Fw
Crystal size (mm)
Crystal colour and habit
Crystal system
Space group
C33H22BO10PRu3W
1107.35
0.21×0.21×0.23
Orange cube
Orthorhombic
Pbca
Unit cell dimensions
,
a (A)
19.539(4)
10.727(2)
33.076(7)
6933(2)
8
,
b (A)
,
c (A)
The original synthesis of HRu3W(h5-Cp)(CO)11BH
[4] proceeded by the reaction of HRu3(CO)9BH4 or
HRu3(CO)9B2H5 with [(h5-Cp)W(CO)3]2. Since the
preparation of HRu3(CO)8(PPh3)B2H5 is facile [8], we
decided to use a parallel strategy to attempt to prepare
HRu3W(h5-Cp)(CO)10(PPh3)BH. Photolysis of a THF
3
,
V (A )
Z
Dcalc (g cm−3
Radiation
)
2.122
Mo–Ka
,
(u=0.71073 A)
293(2)
Temperature (K)
Diffractometer
2q range (°)
Bruker P4
2.08–22.49
4512, 1893
8.99, 17.45
1.107
solution
of
HRu3(CO)8(PPh3)B2H5
and
[(h5-
Independent reflections (observed [4|(Fo)])
Cp)W(CO)3]2 resulted in the formation of HRu3W(h5-
Cp)(CO)10(PPh3)BH (2), in low yield. Evidence for its
formation came from the appearance in the FABMS of
a parent ion with correct isotopomer distribution at
m/z=1106 with loss of ten CO ligands. In the 11B-
NMR spectrum of the product, a broad signal at l
+129 was indicative of the boron atom residing in a
butterfly-shaped tetrametal core; the corresponding res-
onance for 1 is l +132. Attempts to improve the yield
of 2 via this reaction route, however, were unsuccessful.
The most fruitful approach to the synthesis of com-
pound 2 was to activate compound 1 with respect to
ligand substitution by using the well-tested methodol-
ogy of CO replacement by the labile ligand MeCN. The
reaction of 1 with Me3NO and MeCN was monitored
by using IR spectroscopy, and when absorptions due to
1 had been virtually fully replaced by those of a new
compound (assumed to be an MeCN derivative), the
reaction mixture was added to PPh3. The reaction was
monitored by IR spectroscopy, and was judged to be
complete after 1.5 h. The major product of this reaction
was HRu3W(h5-Cp)(CO)10(PPh3)BH (2); the reaction
was reproducible although yields were rather varied,
R(F), R(wF2) (%)
Goodness-of-fit
Data:parameter ratio
Largest difference peak and hole (e A
16.8
1.76 and −1.99
–3
,
)
Scheme 1.

92
C.E. Housecroft et al. / Journal of Organometallic Chemistry 609 (2000) 89–94
Scheme 2.
but typically about 50%. Some starting cluster 1 was
always obtained back, as well as low yields of the
disubstituted cluster HRu3W(h5-Cp)(CO)9(PPh3)2BH
(3). The FAB mass spectrum and 11B-NMR spectrum
of 2 obtained by this route were consistent with those
recorded for the product of the reaction of
HRu3(CO)8(PPh3)B2H5 and [(h5-Cp)W(CO)3]2 (see
above). The 31P-NMR spectrum of 2 exhibited a single
peak at l +37.5; absence of any satellite peaks indi-
cated that the phosphine ligand was bound to Ru
rather than W. The 1H-NMR spectrum was particularly
diagnostic. A signal at l −20.4 was characteristic of a
hydride bridging two hinge Ru atoms. That this signal
was a doublet with J=2.3 Hz indicated long range
31Pꢀ1H coupling and was of a magnitude consistent
As mentioned earlier, the site of second substitution
on going from HRu4(CO)11(PPh3)BH2 to HRu4(CO)10-
(PPh3)2BH2 is the second wingtip Ru atom for the case
of L=PPh3, but a hinge Ru atom for L=Ph2PH.
For this boron-containing cluster, other hinge substitu-
tion has only been observed in the case of a didentate
ligand with short backbone, for example, bis-
(diphenylphosphino)ethane in which a Ru(wingtip)ꢀ
Ru(hinge) bridging mode is adopted. The disubstituted
derivative HRu3W(h5-Cp)(CO)9(PPh3)2BH (3), was
only isolated in low yield. The FAB mass spectrum
exhibited a parent ion (with an isotopic distribution
matching that simulated) at 1342. In the 11B-NMR
spectrum, a signal at l +129 indicated that the
boron environment had not been perturbed on going
from 2 to 3. No well resolved 31P-NMR spectrum could
with our previous observations in HRu4(CO)12−x
-
(PPh3)xBH2 (x=1 or 2) for coupling between a wingtip
bound PR3 ligand and the hinge hydride. Further, the
signal due to the RuꢀHꢀB bridging hydrogen was ob-
served at l −5.6, and was significantly shifted with
respect to that in the parent compound 1 (l −6.6). We
return to this diagnostic shift in signal later. Confirma-
tion of the substitution position came from a single
crystal structure determination of 2.
1
be obtained, but signals in the H-NMR spectrum were
diagnostic. A broad signal at l –5.6 was assigned to
the RuꢀHꢀB hydrogen atom, and by comparison
with the corresponding signals in compounds
1
and 2, we could conclude that a {(CO)2(PPh3)-
Suitable crystals of 2 were grown from a cooled
solution of 2 in CH2Cl2. Fig. 1 shows the molecular
structure of 2, and selected bond distances and angles
are given in Table 2. The retention of the Ru3W
butterfly framework on going from 1 (which has also
been structurally characterized [4]) to 2 was confirmed,
as was the retention of the W(CO)2(h5-Cp) fragment in
a wingtip site. As in 1, the two W-attached CO ligand
lean over towards the B atom, the latter being in a
semi-interstitial position with respect to the metal core.
,
The B atom lies 0.26 A above the Ru(wingtip)ꢀ
W(wingtip) axis. All CO ligands are terminally attached
and bond parameters are unexceptional. The PPh3 lig-
and occupies an equatorial wingtip site on atom Ru(3),
and this site preference matches that in HRu4(CO)11-
(PPh3)BH2 [12]. It is also consistent with the small
J(PH) coupling constant observed for the Ru(hinge)ꢀ
HꢀRu(hinge) hydride (see above).
Fig. 1. Molecular structure of HRu3W(h5-Cp)(CO)10(PPh3)BH (2).
Cluster hydrogen atoms were not located; phenyl and CpꢀH atoms
are omitted.

C.E. Housecroft et al. / Journal of Organometallic Chemistry 609 (2000) 89–94
93
Table 2
ond PPh3 ligand coordinates to a hinge Ru atom, cis to
the RuꢀHꢀRu hydrogen atom. This signal would be
expected to be a doublet of doublets, but no coupling
between the Ru(wingtip)ꢀP atom and the hydride could
,
Selected bond lengths (A) and angles (°) in 2
Bond distances
W(1)ꢀRu(1)
W(1)ꢀB(1)
Ru(1)ꢀRu(3)
Ru(2)ꢀRu(3)
Ru(3)ꢀP(1)
2.986(3)
2.12(3)
2.899(4)
2.857(4)
2.357(9)
W(1)ꢀRu(2)
Ru(1)ꢀRu(2)
Ru(1)ꢀB(1)
Ru(2)ꢀB(1)
Ru(3)ꢀB(1)
2.981(3)
2.834(3)
2.18(3)
2.23(3)
2.12(3)
be
resolved.
In
the
related
compound
HRu4(CO)10(Ph2PH)2BH2, the hinge hydride also ap-
peared as a doublet (J=11.5 Hz) and, moreover, in
HRu4(CO)11(Ph2PH)BH2, no coupling between the
Ru(wingtip)ꢀP atom and the hydride could be resolved
[13]. Using the numbering scheme in Scheme 1 for
structure 1, we therefore propose a substitution pattern
in HRu3W(h5-Cp)(CO)9(PPh3)2BH of (1,6), (1,9), (1,5)
or (1,8); of these the (1,5) distribution would seem to be
unlikely on steric grounds.
Bond angles
Ru(1)ꢀW(1)ꢀRu(2)
Ru(2)ꢀW(1)ꢀB(1)
W(1)ꢀRu(1)ꢀRu(3)
W(1)ꢀRu(1)ꢀB(1)
Ru(3)ꢀRu(1)ꢀB(1)
W(1)ꢀRu(2)ꢀRu(3)
W(1)ꢀRu(2)ꢀB(1)
Ru(3)ꢀRu(2)ꢀB(1)
Ru(1)ꢀRu(3)ꢀP(1)
Ru(1)ꢀRu(3)ꢀB(1)
P(1)ꢀRu(3)ꢀB(1)
Ru(3)ꢀB(1)ꢀRu(1)
Ru(3)ꢀB(1)ꢀRu(2)
Ru(1)ꢀB(1)ꢀRu(2)
56.71(7)
48.3(8)
91.24(10) Ru(2)ꢀRu(1)ꢀRu(3)
45.1(7)
46.6(7)
92.16(10) Ru(1)ꢀRu(2)ꢀRu(3)
45.1(7)
47.2(7)
110.6(2)
48.6(8)
118.4(8)
84.8(10)
82.2(10)
80.0(8)
Ru(1)ꢀW(1)ꢀB(1)
W(1)ꢀRu(1)ꢀRu(2)
46.9(8)
61.56(9)
59.77(10)
50.8(8)
61.73(9)
61.24(11)
49.3(8)
58.99(8)
167.8(2)
50.6(8)
167.6(14)
88.0(10)
86.6(10)
Ru(2)ꢀRu(1)ꢀB(1)
W(1)ꢀRu(2)ꢀRu(1)
Ru(1)ꢀRu(2)ꢀB(1)
Ru(1)ꢀRu(3)ꢀRu(2)
Ru(2)ꢀRu(3)ꢀP(1)
Ru(2)ꢀRu(3)ꢀB(1)
Ru(3)ꢀB(1)ꢀW(1)
W(1)ꢀB(1)ꢀRu(1)
W(1)ꢀB(1)ꢀRu(2)
When assigning sites of PR3 substitution in a cluster,
the presence of hydrides is particularly useful in terms
1
of using H-NMR spectroscopy and observed values of
J(PH) to aid the assignment of sites of substitution.
One of the problems with boron-attached hydrogen
atoms is that they give rise to broad signals in the
1
1H-NMR spectrum (Fig. 2); in the absence of H{11B}
decoupling experiments, it is not possible to resolve
31Pꢀ1H coupling in such signals. We have now prepared
a series of phosphine substituted homo- and het-
erometallic boride clusters containing M4 butterfly
cores hosting a semi-interstitial boron atom, and have
crystallographic data on representative members of the
series which provide firm evidence for the location of
the PR3 substituents. Inspection of the data in Table 3
shows clearly that the chemical shift of the
Ru(wingtip)ꢀHꢀB hydrogen atom is sensitive to the
presence of a Ru(wingtip) PR3 substituent attached to
the same Ru atom, while the shift of the signal due to
the Ru(hinge)ꢀHꢀRu(hinge) hydride only responds to
substitution at one of the Ru(hinge) atoms. While these
results are not surprising in terms of the change in
electron density at the Ru centre that must accompany
PR3-for-CO substitution, Table 3 brings together a
Fig. 2. Part of the 1H-NMR spectrum (400 MHz, CDCl3, 298 K) of
compound 2 showing the signals due to the cluster-bound H atoms.
RuꢀHꢀB} connectivity pattern was present for the
1
wingtip Ru atom. A doublet in the H-NMR spectrum
at l −19.5 showed a coupling of 8.5 Hz typical of
cis-PH coupling and, therefore, indicated that the sec-
Table 3
1H-NMR spectroscopic data for cluster-bound H atoms in a series of phosphine substituted M4B-butterfly clusters
Compound
Site of substitution
l Ru(wingtip)ꢀHꢀB
l Ru(hinge)ꢀHꢀRu(hinge)
and (J(PH), Hz)
Ref.
HRu4(CO)12BH2
HRu4(CO)11(PPh3)BH2
HRu4(CO)10(PPh3)2BH2
HRu4(CO)11(PPh2H)BH2
HRu4(CO)10(PPh2H)2BH2
HRu3W(h5-Cp)(CO)11BH
HRu3W(h5-Cp)(CO)10(PPh3)BH
HRu3W(h5-Cp)(CO)9(PPh3)2BH
HRu3Rh(h5-Cp*)(CO)9BH2
HRu3Rh(h5-Cp*)(CO)8(PPh3)BH2
−8.4 (2H)
−7.5; −8.6
−7.5 (2H)
−7.9; −8.5
−21.2
[14,15]
[12]
[12]
[13]
[13]
Ru(wingtip)
2Ru(wingtip)
Ru(wingtip)
−21.1 (2)
−21.1 (2.4)
−21.1 a
Ru(wingtip); Ru(hinge) −8.0; −8.5
−6.6
−20.4 a (11.5)
−20.4
[4]
Ru(wingtip)
Ru(wingtip); Ru(hinge) −5.6
−9.6 (2H) b
−4.9
−5.6
−20.4 (2.3)
−19.5 (8.5)
−20.3
This work
This work
[6]
Ru(wingtip)
−14.4 (14); −20.6 a
[6]
a No 31Pꢀ1H coupling was resolved between the Ru(wingtip) phosphine and the Ru(hinge)ꢀHꢀRu(hinge) hydride.
b One broad signal assigned to both RhꢀHꢀB and RuꢀHꢀB.

94
C.E. Housecroft et al. / Journal of Organometallic Chemistry 609 (2000) 89–94
useful set of data emphasizing a chemical shift correla-
tion that can aid structural assignment. In the case of
HRu3Rh(h5-Cp*)(CO)9BH2, substitution of CO by
PPh3 occurs (in line with related systems) at the wingtip
Ru atom, but is accompanied by the migration of the
RhꢀHꢀB cluster hydrogen atom to the metal frame-
work. This is reflected, not only in the appearance of an
tion for a grant (CHE 9007852) towards the purchase
of a diffractometer at the University of Delaware.
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1
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4. Supplementary material
Crystallographic data for the structural analysis have
been deposited with the Cambridge Crystallographic
Data Centre, CCDC no. 140104. Copies of this infor-
mation 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).
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Acknowledgements
We thank the EPSRC for a grant (to D.M.N.), the
University of Basel, and the National Science Founda-
.