The first examples of η5-bonding of a carbaborylphosphine ligand to transition metals. Synthesis and characterisation of 7-{PPh2AuPPh3}-8-Ph-7,8-nido-C2B 9H10, 1-{PPh2AuCl}-2-Ph-3-(p-cymene)-3,1,2-pseudocloso-RuC 2B9H9

Article abstract of DOI:10.1016/S0022-328X(98)00651-2

The closo carbaborylmonophosphine 1-PPh₂-2-Ph-1,2-closo-C₂B₁₀H₁₀ is deboronated by reaction with ClAuPPh₃ in refluxing ethanol to afford the zwitterionic compound 7-{PPh₂AuPPh₃}-8-Ph-7,8-nido-C₂B ₉H₁₀, characterised by NMR spectroscopy and X-ray crystallography. Deprotonation of this species using NaH in THF followed by reaction with either [(p-cymene)RuCl₂]₂ or [(η-C₅Me₅)RhCl₂]₂ yields the compounds 1-{PPh₂AuCl}-2-Ph-3-(p-cymene)-3,1,2-RuC₂B ₉H₉ and 1-{PPh₂AuCl}-2-Ph-3-(η-C₅Me ₅)-3,1,2-RhC₂B₉H₉, respectively. These latter products, which on the basis of ¹¹B-NMR spectroscopy and (in the first case) a single crystal diffraction analysis, have pseudocloso structures, are the first reported examples of compounds in which a carbaborylphosphine ligand is η⁵-bonded to a transition metal.

Full text of DOI:10.1016/S0022-328X(98)00651-2

Journal of Organometallic Chemistry 573 (1999) 165–170
The first examples of p5-bonding of a carbaborylphosphine ligand to
transition metals. Synthesis and characterisation of
7-{PPh2AuPPh3}-8-Ph-7,8-nido-C2B9H10,
1-{PPh2AuCl}-2-Ph-3-(p-cymene)-3,1,2-pseudocloso-RuC2B9H9 and
1,2
1-{PPh2AuCl}-2-Ph-3-(p-C5Me5)-3,1,2-pseudocloso-RhC2B9H9
M. Anna McWhannell a, Georgina M. Rosair a, Alan J. Welch a,*, Francesc Teixidor 3,b
Clara Vin˜as b
,
a Department of Chemistry, Heriot-Watt Uni6ersity, Edinburgh EH14 4AS, UK
b ICMAB-CSIC, Campus de la Uni6ersitat Auto`noma de Barcelona, 08193 Bellaterra, Barcelona, Spain
Received 26 May 1998
Abstract
The closo carbaborylmonophosphine 1-PPh2-2-Ph-1,2-closo-C2B10H10 is deboronated by reaction with ClAuPPh3 in refluxing
ethanol to afford the zwitterionic compound 7-{PPh2AuPPh3}-8-Ph-7,8-nido-C2B9H10, characterised by NMR spectroscopy and
X-ray crystallography. Deprotonation of this species using NaH in THF followed by reaction with either [(p-cymene)RuCl2]2 or
[(p-C5Me5)RhCl2]2 yields the compounds 1-{PPh2AuCl}-2-Ph-3-(p-cymene)-3,1,2-RuC2B9H9 and 1-{PPh2AuCl}-2-Ph-3-(p-
C5Me5)-3,1,2-RhC2B9H9, respectively. These latter products, which on the basis of 11B-NMR spectroscopy and (in the first case)
a single crystal diffraction analysis, have pseudocloso structures, are the first reported examples of compounds in which a
carbaborylphosphine ligand is p5-bonded to a transition metal. © 1999 Elsevier Science S.A. All rights reserved.
Keywords: Carbaborylphosphine ligand; NMR spectroscopy; Diffraction
1. Introduction
not normally represented on the traditional Wade–
Williams structural matrix; (iii) they can undergo low-
temperature polytopal isomerisation [3] rendering
possible experimental study [4] of the isomerisation
process that has been the subject of intense theoretical
interest over a number of years, including important
contributions from Brian Johnson and co-workers. [5]
An important family of carbaboranes carrying steri-
cally demanding exo-bonded substituents are the
carbaborylphosphines, with carbaborylmonophosphi-
nes [6] and carbaboryldiphosphines [7] both being well
known. Unfortunately, deboronation of these closo
species (to prepare nido ligands suitable for complex
formation with transition metals) by the conventional
method (OH−/OR−) typically leads to cleavage of the
Ccage–P bond(s).
There is much current interest in the chemistry of
heteroboranes with bulky substituents attached for a
number of reasons; (i) such compounds can adopt
exo-nido instead of more crowded closo structures (and
as such display homogeneous catalytic activity) [1]; (ii)
they can distort into unusual pseudocloso geometries [2]
* Corresponding author. Tel.: +44 131 4513217; fax: +44 131
4513180; e-mail: a.j.welch@hw.ac.uk
1 Steric effects in Heteroboranes. Part 20. For part 19 see reference
[4]b.
2 Dedicated to Professor Brian Johnson on the occasion of his 60th
birthday.
3 Also corresponding author. Tel.: +34 3 580 1853; fax: +34 3
580 5729; e-mail: teixidor@icmab.es
0022-328X/99/$ - see front matter © 1999 Elsevier Science S.A. All rights reserved.
PII S0022-328X(98)00651-2

166
M.A. McWhannell et al. / Journal of Organometallic Chemistry 573 (1999) 165–170
Fig. 1. Perspective view of 1. Displacement ellipsoids are drawn at the 30% probability level, except for H atoms which have an artificial radius
for clarity.
Recently, however, successful deboronation of 1,2-
(PPh2)2-1,2-closo-C2B10H10 with CuI [8] and AuI [9]
species under base-free conditions has been reported.
The products of these reactions, 7,8-{(PPh2)2MPR3}-
7,8-nido-C2B9H10 are in principle able to function as
p5 ligands to metals following cage deprotonation,
but steric pressure from the two PPh2 units located
on the open ligand face has so far prevented this
from being realised.
trum are seen, in addition to resonances between −6
and −22 ppm, two resonances at low frequency
(−31 and −35 ppm) characteristic of a nido species.
The 31P{1H} spectrum reveals two doublets (2JPP
=
320 Hz) the higher frequency of which is the broader
and tentatively assigned to Ccage–P.
Herein we report similar decapitation of the
carbaborylmonophosphine
1-PPh2-2-Ph-1,2-closo-C2
B10H10 to afford 7-{PPh2AuPPh3}-8-Ph-7,8-nido-C2B9
H10 (1). Deprotonation of 1 followed by reaction with
[(p-cymene)RuCl2]2 or [(p-C5Me5)RhCl2]2 affords the
first examples of a carbaborylphosphine ligand bond-
ing in p5 fashion to transition metals.
2. Results and discussion
The molecular structure of 1 is shown in Fig. 1,
and selected interatomic distances and interbond an-
gles appear in Table 1. Successful deboronation of
the closo carbaborylphosphine is confirmed, and the
C(7)–C(8) distance in the carbaborane open face is
Heating to reflux an ethanolic solution of 1-PPh2-2-
Ph-1,2-closo-C2B10H10 [10] and ClAuPPh3 affords the
zwitterionic species 7-{PPh2AuPPh3}-8-Ph-7,8-nido-
C2B9H10 (1) in high yield. Compound 1 was charac-
terised by multinuclear NMR spectroscopy, mass
spectrometry, elemental analysis and a single-crystal
X-ray diffraction study. In the 11B{1H}-NMR spec-
˚
1.591(9) A. The H atom bridging the B(9)–B(10) edge
appears to do so asymmetrically, H(B)–B(9) 1.56(9)
˚
˚
A, H(B)–B(10) 1.14(9) A. The phenyl substituent at

M.A. McWhannell et al. / Journal of Organometallic Chemistry 573 (1999) 165–170
167
C(8) adopts a conformation defined by q=6.5(9)°
[11] and the stereochemistry at Au in the {PPh2AuP-
Ph3} substituent at C(7) is approximately linear,
˚
174.68(8)°. Au–P(1) is 2.320 (2) A and Au–P(2)
˚
2.312(2) A. Preliminary details of the related com-
pound 7-{PPh2AuPPh3}-8-SCH2Ph-7,8-nido-C2B9H10
have recently been reported. [12]
Deprotonation [H(B)] of 1 with NaH in THF
yields
Na[7-{PPh2AuPPh3}-8-Ph-7,8-nido-C2B9H9].
Treatment of this salt with [(p-cymene)RuCl2]2 in the
same solvent affords the deep red compound 1-
{PPh2AuCl}-2-Ph-3-(p-cymene)-3,1,2-pseudocloso-
RuC2B9H9 (2) in moderate yield following work-up
involving preparative TLC. In the 11B{1H}-NMR
spectrum, 2 reveals seven resonances (two coinci-
dences) between +36 and −19 ppm., the weighted
average 11B chemical shift, Bl(11B)\, being +9.88
ppm. The equivalent value in 1,2-Ph2-3-(p-cymene)-
3,1,2-pseudocloso-RuC2B9H9 [2] is +5.58 ppm. How-
ever, Bl(11B)\for 2 is fully consistent with a
pseudocloso geometry once the differing Bl(11B)\
values of 1,2-Ph2-1,2-closo-C2B10H10 (−10.66 ppm)
Fig. 2. Perspective view of 2, showing only one component of the
disordered isopropyl group for the sake of clarity. Displacement
ellipsoids as in Fig. 1.
and 1-PPh2AuCl-2-Ph-1,2-closo-C2B10H10 [13] (−7.75
ppm) are taken into account.
Table 1
˚
Selected interatomic distances (A) and interbond angles (°) for 1
AuꢀP(2)
2.312(2) AuꢀP(1)
2.320(2)
1.816(8)
1.813(9)
1.822(9)
1.774(14)
1.778(13)
1.742(11)
1.771(13)
1.722(10)
1.770(13)
1.775(14)
1.77(2)
1.83(2)
1.77(2)
1.630(11)
1.651(12)
1.81(2)
P(1)ꢀC(111)
P(1)ꢀC(7)
P(2)ꢀC(201)
B(1)ꢀB(2)
B(1)ꢀB(6)
B(1)ꢀB(5)
B(2)ꢀB(6)
B(2)ꢀB(11)
B(3)ꢀC(7)
B(4)ꢀC(8)
B(4)ꢀB(9)
B(5)ꢀB(10)
B(6)ꢀB(11)
C(7)ꢀC(8)
C(8)ꢀC(81)
B(9)ꢀB(10)
1.814(8) P(1)ꢀC(101)
1.818(8) P(2)ꢀC(221)
1.817(9) P(2)ꢀC(211)
1.759(13) B(1)ꢀB(4)
1.78(2)
B(1)ꢀB(3)
1.811(14) B(2)ꢀC(7)
1.759(13) B(2)ꢀB(3)
1.776(14) B(3)ꢀC(8)
1.739(10) B(3)ꢀB(4)
1.706(11) B(4)ꢀB(5)
1.789(14) B(5)ꢀB(9)
1.78(2)
B(5)ꢀB(6)
1.746(13) B(6)ꢀB(10)
1.591(9) C(7)ꢀB(11)
1.513(10) C(8)ꢀB(9)
1.828(14) B(10)ꢀB(11)
P(2)ꢀAuꢀP(1)
174.68(8)
C(111)ꢀP(1)ꢀC(101) 106.9(3)
C(111)ꢀP(1)ꢀC(7)
C(111)ꢀP(1)ꢀAu
C(7)ꢀP(1)ꢀAu
105.8(4)
109.8(3)
116.8(2)
C(101)ꢀP(1)ꢀC(7)
C(101)ꢀP(1)ꢀAu
107.6(3)
109.5(3)
C(221)ꢀP(2)ꢀC(201) 107.9(4)
C(201)ꢀP(2)ꢀC(211) 105.4(4)
C(221)ꢀP(2)ꢀC(211) 105.2(4)
C(221)ꢀP(2)ꢀAu
C(211)ꢀP(2)ꢀAu
B(11)ꢀC(7)ꢀP(1)
B(2)ꢀC(7)ꢀP(1)
C(81)ꢀC(8)ꢀB(9)
C(81)ꢀC(8)ꢀB(4)
B(9)ꢀC(8)ꢀB(4)
C(7)ꢀC(8)ꢀB(3)
B(4)ꢀC(8)ꢀB(3)
109.5(3)
115.7(3)
120.0(5)
119.4(5)
119.0(6)
120.6(6)
64.4(6)
C(201)ꢀP(2)ꢀAu
C(8)ꢀC(7)ꢀP(1)
B(3)ꢀC(7)ꢀP(1)
C(81)ꢀC(8)ꢀC(7)
C(7)ꢀC(8)ꢀB(9)
C(7)ꢀC(8)ꢀB(4)
C(81)ꢀC(8)ꢀB(3)
B(9)ꢀC(8)ꢀB(3)
112.6(3)
116.4(5)
114.8(5)
119.8(6)
109.1(6)
111.4(6)
117.7(6)
115.6(6)
63.2(4)
62.2(5)

168
M.A. McWhannell et al. / Journal of Organometallic Chemistry 573 (1999) 165–170
The pseudocloso nature of 2 is confirmed by a crystal-
carbaborylphosphine ligands. Previously, all transition
metal complexes of carbaborylphosphines have either
involved exo-metal fragments [14] or simple endo bridg-
ing ones [9]. In the case of compounds 2 and 3 we believe
that having a single phosphine unit as substituent to the
cage allows formation of p5-metal complexation since the
carbaborane is not able to function as a chelating ligand
and has (at least relative to [7,8-(PPh2)2-7,8-nido-
C2B9H9]2−) reduced steric blocking of the open ligand
face. Nevertheless, there is clearly sufficient intramolec-
ular crowding in 2 and 3 to distort the cluster geometries
into pseudocloso forms.
Current studies are directed towards the synthesis of
analogous species in which the P lone pair of electrons
is not co-ordinated to an exo-metal fragment, and to a
study of the polytopal isomerisations of this family of
molecules. Since such rearrangements are expected to
occur at relatively low temperatures they may provide
experimental data by which to asses the various isomeri-
sation mechanisms previously suggested by Johnson and
others.
lographic study. Fig. 2 presents a perspective view of one
molecule and demonstrates the atomic numbering
scheme used. Table 2 provides a summary of key
molecular parameters. The C(1)···C(2) separation,
˚
˚
2.481(19) A, and Ru(3)···B(6) separation, 2.940(14) A,
are typical for a pseudocloso carbametallaborane. The
distortion results from intramolecular steric crowding,
brought about in this case by the requirement of the Ph
substituent on C(2) to adopt a high q conformation,
63.9(20)°, due to the presence of the capping {Ru(p-
cymene)} unit. The presence of the {AuCl} fragment
bonded to the P lone pair of electrons in 2 is unexpected,
with the source of the Cl clearly the metal substrate.
˚
P–Au and Au–Cl distances, 2.244(4) and 2.285(4) A,
respectively, and the P–Au–Cl angle, 176.1(2)°, are
typical. [13] Interestingly, one p-cymene ring H atom
resonates at unusually high frequency (7.2 ppm) in the
1H-NMR spectrum, ascribed to the adjacency of the
{AuCl} unit.
Similarly, reaction of Na[7-{PPh2AuPPh3}-8-Ph-7,8-
nido-C2B9H9] with [(p-C5Me5)RhCl2]2 in THF yields
orange
1-{PPh2AuCl}-2-Ph-3-(p-C5Me5)-3,1,2-closo-
RhC2B9H9 (3). Although diffraction-quality crystals of 3
proved to be elusive, its pseudocloso nature is clearly
demonstrated by a Bl(11B)\value of +11.17 ppm.
Compounds 2 and 3 represent the first reported
examples of p5-bonded transition metal complexes of
3. Experimental
3.1. Synthesis and spectroscopy
All syntheses were performed under N2 atmospheres
using standard Schlenk techniques, with some subse-
quent manipulation in the open laboratory. Solvents
were freshly distilled from appropriate drying agents.
NMR spectra were recorded from CDCl3 solutions at r.t.
on a Bruker AC200 (1H, 200.1 MHz; 11B, 128.4 MHz;
31P, 162.0 MHz) spectrometer, and chemical shifts are
quoted relative to external TMS, BF3.OEt2 and H3PO4,
respectively. Elemental analyses were determined on an
Exeter Analytical 440 microanalyser by the Departmen-
tal service at H-WU.
Table 2
˚
Selected interatomic distances (A) and angles (°) for 2
Au(1)ꢀP(1)
P(1)ꢀC(11)
P(1)–C(1)
2.244(4)
1.801(13) P(1)ꢀC(41)
1.858(13) C(1)ꢀC(2)
Au(1)ꢀCl(1)
2.285(4)
1.83(2)
2.42(2)
1.64(2)
2.170(14)
1.60(2)
1.72(2)
2.189(14)
2.21(2)
2.219(14)
2.331(13)
2.389(12)
1.85(2)
1.76(2)
1.85(2)
1.91(2)
1.82(2)
1.75(2)
1.76(2)
1.71(3)
1.80(2)
C(1)–B(5)
1.62(2)
1.72(2)
1.49(2)
1.64(2)
2.136(11) Ru(3)ꢀB(4)
2.207(14) Ru(3)ꢀB(7)
2.209(14) Ru(3)ꢀC(32)
2.251(12) Ru(3)ꢀC(34)
2.341(14) Ru(3)ꢀC(33)
1.77(2)
1.87(2)
1.80(2)
1.80(2)
1.81(2)
1.84(2)
1.78(2)
1.78(2)
1.73(2)
C(1)ꢀB(4)
C(1)ꢀRu(3)
C(2)ꢀB(11)
C(2)ꢀB(6)
C(1)ꢀC(6)
C(2)ꢀC(21)
C(2)ꢀB(7)
C(2)ꢀRu(3)
Ru(3)ꢀC(31)
Ru(3)ꢀB(8)
Ru(3)ꢀC(35)
Ru(3)ꢀC(30)
B(4)ꢀB(8)
The starting materials 1-PPh2-2-Ph-1,2-closo-
C2B10H10 [10], ClAuPPh3 [15], [(p-cymene)RuCl2]2 [16]
and [(p-C5Me5)RhCl2]2 [17] were prepared by literature
methods or slight variants thereof.
B(4)ꢀB(9)
B(5)ꢀB(10)
B(5)ꢀB(6)
B(6)ꢀB(10)
B(7)ꢀB(8)
B(8)ꢀB(9)
B(9)ꢀB(12)
B(10)ꢀB(11)
B(11)ꢀB(12)
B(4)ꢀB(5)
B(5)ꢀB(9)
3.2. Synthesis of 7-{PPh2AuPPh3}-8-Ph-7,
8-nido-C2B9H10 (1)
B(6)ꢀB(11)
B(7)ꢀB(12)
B(7)ꢀB(11)
B(8)ꢀB(12)
B(9)ꢀB(10)
B(10)ꢀB(12)
A solution of 1-PPh2-2-Ph-1,2-closo-C2B10H10 (0.05 g,
1.24 mmol) in degassed EtOH (10 ml) was added to a
stirring suspension of ClAuPPh3 (0.61 g, 1.24 mmol) in
the same solvent (30 ml) and the mixture heated to reflux
for 2 h. Volatiles were removed in vacuo and CH2Cl2 (20
ml) added to the resultant solid. After filtration through
Celite (2 cm) further removal of solvent afforded a white
solid. This was washed with EtOH (2×10 ml) and dried
in vacuo to yield 0.083 g (78%) of the product, 7-
{PPh2AuPPh3}-8-Ph-7,8-nido-C2B9H10 (1).
P(1)ꢀAu(1)ꢀCl(1) 176.1(2)
C(11)ꢀP(1)ꢀC(1) 108.0(6)
C(11)ꢀP(1)ꢀAu(1) 112.7(5)
C(11)ꢀP(1)ꢀC(41) 106.3(7)
C(41)ꢀP(1)ꢀC(1) 106.1(6)
C(41)ꢀP(1)ꢀAu(1) 108.1(5)
C(1)ꢀP(1)ꢀAu(1)
B(4)ꢀC(1)ꢀP(1)
B(6)ꢀC(1)ꢀRu(3)
B(6)ꢀC(2)ꢀRu(3)
115.1(4)
129.6(9)
97.4(8)
98.9(8)
B(5)ꢀC(1)ꢀP(1)
B(6)ꢀC(1)ꢀP(1)
P(1)ꢀC(1)ꢀRu(3)
C(2)ꢀRu(3)ꢀC(1)
116.9(10)
114.2(9)
118.8(6)
70.4(5)

M.A. McWhannell et al. / Journal of Organometallic Chemistry 573 (1999) 165–170
169
Table 3
Calcd. for C38H40AuB9P2; C 53.5, H 4.72%. Found;
Crystal data and details of data collection and refinement
C 53.2, H 4.75%.
1
NMR; H l 8.08-6.45 (Ph) ppm. 31P{1H} l 55.9 (d,
Compound 1
Compound 2
Red plate
1P) and 44.2 (d, 1P, 2JPP 320 Hz) ppm. 11B{1H} l −6.1
(2B), −8.35 (2B), −13.16 (1B), −17.41 (1B), −21.86
(1B), −30.94 (1B) and −34.52 (1B) ppm.
Crystal colour,
habit
Crystal size (mm) 0.50×0.32×0.12
Colourless plate
0.61×0.42×0.08
Formula
M
System
C38H40AuB9P2
852.90
Triclinic
C30H38AuB9ClPRu.CHCl3
979.72
Monoclinic
P21/n
3.3. Synthesis of 1-{PPh2AuCl}-2-Ph-3-(p-cymene)
-3,1,2-pseudocloso-RuC2B9H9 (2)
(
Space group
Unit cell dimen-
sions
P1
A solution of compound 1 (0.15 g, 0.176 mmol) in
THF (15 ml) was added to a stirring suspension of
NaH (ca. 0.02 g, 0.88 mmol) in the same solvent (10
ml). After 1 h undissolved material was allowed to
settle and the supernatant solution was transferred by
cannula to a stirring solution of [(p-cymene)RuCl2]2
(0.053 g, 0.088 mmol) in THF (10 ml). After further
stirring for 1 h volatiles were removed in vacuo to
reveal a red/brown solid. CH2Cl2 (10 ml) was added
and the mixture filtered through Celite (2 cm) and
concentrated to ca. 2 ml. Preparative TLC on silica
using CH2Cl2/EtOAc (4:1) as eluant afforded two mo-
bile bands. The slower moving of these was collected
(by IR spectroscopy the faster moving band does not
contain a heteroborane) and subsequently shown by
31P{1H}-NMR spectroscopy to be a 1:2 mixture of
7-{PPh2AuPPh3}-8-Ph-9,10-(v-AuPPh3)-7,8-nido-C2B9
H9 [18] and the target material 1-{PPh2AuCl}-2-Ph-3-
(p-cymene)-3,1,2-pseudocloso-RuC2B9H9 (2). Recrys-
tallisation by slow diffusion of 60/80 petroleum ether
and a CHCl3 solution of 2 afforded 0.016 g (21%) of
product as red plates.
˚
a (A)
11.060(2)
13.429(3)
15.078(3)
113.568(11)
95.98(2)
107.549(8)
1891.4(7)
2
13.626(2)
20.5341(10)
13.8129(11)
90.00
98.084(12)
90.00
3826.4(7)
4
1.701
˚
b (A)
˚
c (A)
h (°)
i (°)
k (°)
3
˚
U (A )
Z
Dcalc
1.498
4.00
v (Mo–Kh)
4.57
(mm−1
)
qorientation (°)
qdata collection (°) 1.5–25.00
hkl range
5.22–12.44
4.91–12.40
1.7–25.00
−15h513; −145 −15h516; −15k524;
k513; −175l517 −165l516
14766
6371
5326
Data measured
Unique dataa
Observed data
[I\2|(I)]
8025
6668
3687
R, wR2 (observed 0.0463, 0.1013
0.0631, 0.1126
data)
Variables
454
469
Emax, Emin
1.190, −1.098
1.097, −0.879
−3
˚
(e A
)
Calcd. for C30H38AuB9ClPRu (crushed, dry powder);
C 41.9, H 4.45%. Found; C 42.1, H 4.48%.
R=SꢀꢀFoꢀ−ꢀFcꢀꢀ/SꢀFoꢀ, wR2=[S[w(Fo2−Fc2)2]/Sw(F2o)2]1/2
,
where
w
−1=[|2c(Fo)2+(aP)2+bP]
where
P=[0.333max{Fo, 0}+
NMR; 1H l 8.35–8.24 (2H, Ph), 7.97–7.24 (13H,
Ph), 7.18 6.02 5.25 and 4.61 (all d, 7Hz, C6H4), 2.34 (d
of q, 7Hz 7Hz, CHMe2), 1.45 (s, 3H, Me), 0.97 (d, 7
Hz, CHMe) and 0.62 (d, 7 Hz, CHMe) ppm. 31P{1H} l
62.4 (s) ppm. 11B{1H} l 35.84 (1B), 22.68 (1B), 17.98
(1B), 15.95 (1B), 7.91 (2B), −0.55 (2B) and −18.22
(1B) ppm.
0.667(Fo)2], S=[S[w(Fo2−F2c)2/(n−p)]1/2 where n is the number of
data and p, the number of parameters.
7.64–7.19 (11H, Ph), and 1.47 (s, 15H, Me) ppm.
31P{1H} l 55.7 (s) ppm. 11B{1H} l 41.26 (1B), 19.01
(2B), 12.84 (1B), 10.80 (1B), 7.81 (2B), −0.02 (1B) and
−17.98 (1B) ppm.
3.4. Synthesis of 1-{PPh2AuCl}-2-Ph-3-
(p-C5Me5)-3,1,2-pseudocloso-RhC2B9H9 (3)
3.5. Crystallographic studies
Similarly, compound 1 (0.15 g, 0.176 mmol) was
deprotonated (NaH) and reacted with [(p-
C5Me5)RhCl2]2 (0.054 g, 0.089 mmol) in THF. Work-
up by column chromatography (15 cm) on silica,
eluting with CH2Cl2/EtOAc (9:1), afforded a single
orange mobile band of 1-{PPh2AuCl}-2-Ph-3-(p-
C5Me5)-3,1,2-pseudocloso-RhC2B9H9 (3). Yield 0.018 g
(12%).
Crystals of 1 and 2 were grown by slow diffusion of
chloroform solutions and 60/80 petroleum ether and
were mounted in epoxy resin glue in a sealed thin-
walled glass capillary. Data were collected at 293 K on
a Siemens P4 diffractometer with the program XS-
CANS [19] by ꢀ scans. Standard reflections were re-
measured every 100 data, and slight crystal decay
(14.5% for 1 and 10% for 2) was found and subse-
quently corrected. Data were further corrected for ab-
sorption by psi scans.
Calcd. for C30H39AuB9ClPRu; C 41.7, H 4.55%.
Found; C 42.1, H 4.83%.
1
NMR; H l 8.14-8.07 (2H, Ph), 7.89–7.86 (2H, Ph),

170
M.A. McWhannell et al. / Journal of Organometallic Chemistry 573 (1999) 165–170
[2] P.T. Brain, M. Bu¨hl, J. Cowie, Z.G. Lewis, A.J. Welch, J. Chem.
Both structures were solved by direct and difference
Soc. Dalton Trans. 231 (1996) 635.
Fourier methods and refined by full-matrix least-
squares against F2. All non-hydrogen atoms were
refined with anisotropic thermal parameters. All exo-
cage, phenyl and methyl H atom positions were calcu-
lated and treated as riding models with isotropic
thermal parameters 1.2, 1.2 and 1.5 times the bound
carbon atom Ueq respectively. The bridging cage H
[3] D.R. Baghurst, R.C.B. Copley, H. Fleischer, D.M.P. Mingos,
G.O. Kyd, L.J. Yellowlees, A.J. Welch, T.R. Spalding, D.
O’Connell, J. Organomet. Chem. 447 (1993) C14.
[4] (a) S. Dunn, G.M. Rosair, Rh. Ll. Thomas, A.S. Weller, A.J.
Welch, Angew. Chem. Int. Ed. Engl. 36 (1997) 645. (b) S. Dunn,
G.M. Rosair, A.S. Weller, A.J. Welch, J. Chem. Soc. Chem.
Commun. (1998) 1065.
[5] Y.V. Roberts, B.F. Johnson, J. Chem. Soc. Dalton Trans. (1994)
749 and references therein.
atom in 1 was found in a difference Fourier map and
positionally refined, with Uiso fixed at 0.05 A .
2
˚
[6] (a) R. Kiveka¨s, R. Sillanpa¨a¨, F. Teixidor, C. Vin˜as, R. Nun˜ez,
Acta Crystallogr. C50 (1994) 2027.(b) R. Kiveka¨s, F. Teixidor,
C. Vin˜as, R. Nun˜ez, Acta Crystallogr. C51 (1995) 1868.
[7] R.P. Alexander, H. Schoeder, Inorg. Chem. 26 (1963) 1107.
[8] F. Teixidor, C. Vin˜as, M.M. Abad, M. Lopez, J. Casabo,
Organometallics 12 (1993) 3766.
There were two orientations of the isopropyl group
on the p-cymene ligand in 2, and all four partial methyl
groups were assigned fixed occupancies of 0.5. Two
positions for each Cl atom were found for the disor-
dered molecule of CHCl3 solvate. One group was as-
signed occupancy factors of 0.75, the other 0.25.
Crystallographic computing was performed on a Pen-
tium 90 MHz PC using the SHELXTL [20] system.
Table 3 lists crystallographic data and further details of
solution and refinement.
[9] O. Crespo, M.C. Gimeno, P.G. Jones, A. Laguna, Inorg. Chem.
35 (1996) 1361.
[10] M.A. McWhannell, G.M. Rosair, A.J. Welch, F. Teixidor, C.
Vina˜s, Acta Crystallogr. C52 (1996) 3135.
[11] J. Cowie, B.D. Reid, J.M.S. Watmough, A.J. Welch, J.
Organomet. Chem. 481 (1994) 283.
[12] R. Bennaki, C. Vin˜as, F. Teixidor, R. Kiveka¨s, R. Sillanpa¨a¨,
Abstracts of First European Conference on Boron Chemistry,
Platja d’Aro, Spain, 1997, p. 61.
[13] M.A. McWhannell, G.M. Rosair, A.J. Welch, Acta Crystallogr.
C54 (1998) 13.
Acknowledgements
[14] F. Teixidor, C. Vin˜as, M.M. Abad, R. Kiveka¨s, R. Sillanpa¨a¨, J.
Organomet. Chem. 509 (1996) 139.
[15] M.I. Bruce, B.K. Nicholson, O. Bin Shawkataly, Inorg. Synth.
26 (1989) 324.
[16] M.A. Bennett, T. -N Huang, T.W. Matheson, A.K. Smith,
Inorg. Synth. 21 (1982) 74.
[17] J.W. Kang, K. Mosely, P.M. Maitlis, J. Am. Chem. Soc. 91
(1969) 5970.
This work was supported by CIRIT (research grant
QFN95-4721) and by NATO (collaborative research
grant CRG 971636). AJW thanks the Callery Chemical
Company for continued support through a generous
gift of decaborane.
[18] M. A. McWhanell, A. J. Welch, unpublished results.
[19] XSCANS. Siemens Analytical Instruments, Madison, Wisconsin,
USA, 1994.
References
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.