Ruthenium (II) complexes of the chelating phosphine borane H2ClB · dppm

Article abstract of DOI:10.1016/j.jorganchem.2005.01.048

Reaction of H₂ClB ? PPh₂CH₂PPh ₂ (H₂ClB ? dppm) with [RuCp*(NCMe)3][BAr4F] (BAr4F=[B{3,5-(CF3)2C6H3}4]-) results in displacement of all three acetonitrile ligands and the formation of [RuCp*(η2-H2ClB·dppm)][BAr4F] (1), which has been characterised crystallographically. Reaction with carbon monoxide results in a change from η² to η¹ of the borane ligand to afford [RuCp*(CO)(η1-H2ClB·dppm)][BAr4F] (2). Compound 1 undergoes H/D exchange under a D₂ atmosphere to afford [RuCp*(η2-D2ClB·dppm)][BAr4F], while 2 does not.

Full text of DOI:10.1016/j.jorganchem.2005.01.048

Journal of Organometallic Chemistry 690 (2005) 2829–2834
www.elsevier.com/locate/jorganchem
Ruthenium (II) complexes of the chelating phosphine
borane H2ClBÆdppm
Nicolas Merle, Christopher G. Frost, Gabriele Kociok-Ko¨hn,
*
Michael C. Willis, Andrew S. Weller
Department of Chemistry, University of Bath, Bath BA2 7AY, UK
Received 11 November 2004; accepted 24 January 2005
Available online 17 March 2005
Abstract
Reaction of H2ClBÆPPh2CH2PPh2 (H2ClBÆdppm) with ½RuCpꢀðNCMeÞ ꢁ½BArFꢁ ðBArF ¼ ½Bf3; 5-ðCF3Þ C6H3g ꢁꢂÞ results in
3
4
4
2
4
displacement of all three acetonitrile ligands and the formation of ½RuCpꢀðg2-H2ClB ꢃ dppmÞꢁ½BAr4Fꢁ (1), which has been character-
ised crꢀystallographically. Reaction with carbon monoxide results in a change from g2 to g1 of the borane ligand to afford
1 undergoes H/D exchange under a D2 atmosphere to afford
½RuCp ðCOÞðg1-H2ClB ꢃ dppmÞꢁ½BArF4 ꢁ (2). Compound
½RuCpꢀðg2-D2ClB ꢃ dppmÞꢁ½BArF4 ꢁ, while 2 does not.
ꢀ 2005 Elsevier B.V. All rights reserved.
Keywords: Ruthenium; Borane; Hemi-labile; Co-ordinatively unsaturated
1. Introduction
Incorporating the borane into a bidentate, chelating
ligand has the effect of stabilising the resulting complex
towards loss of borane, in a similar manner to the stabil-
isation afforded to the Mꢃ ꢃ ꢃH3C linkage in agostic com-
plexes compared with intermolecular r-complexes [6].
Thus, the chelating phosphine borane H3BÆPPh2-
CH2PPh2 (H3BÆdppm) [7] (structure B Scheme 1) forms
stable complexes that do not suffer from spontaneous
decomposition or facile displacement of the Mꢃ ꢃ ꢃ
HB interaction. Nido-Rh(g2-H3BÆdppm)(SB9H10) [8]
Cr(CO)4(g1-H3BÆdppm) [9], [Rh(cod)(g2-H3BÆdppm)]-
[PF6] [10] are examples of such complexes.1 Coordina-
tion compounds of the chelating diborane ligand
B2H4 Æ(PMe3)2 (C) have also been reported, and this li-
gand can either adopt a monodentate or a bidentate
binding mode such as Cr(CO)5{g1-B2H4 Æ(PMe3)2}
[1,11] and [Cu{g2-B2H4 Æ(PMe3)2}2] (I) [12]. We have
Phosphine boranes, such as H3BÆPR3, are valance
isoelectronic with alkanes [1]. This relationship has been
elegantly exploited by Shimoi in the isolation of ana-
logues of elusive transition metal alkane complexes.
For example, r-alkane complexes such as Cr(CO)5 (al-
kane) [2] and ReCp(CO)2(C5H10) [3] have a limited life-
time and have only been characterised spectroscopically;
while the related phosphine borane complexes, such as
Cr(CO)5(H3BÆPMe3) [4] and MnCp(CO)2(H3BÆPMe3)
[5] (structural type A, Scheme 1), are relatively stable
at room temperature allowing them to be crystallo-
graphically characterised. However, these latter com-
plexes are not completely robust and suffer from
spontaneous decomposition, removal of the borane un-
der a vacuum or substitution by another ligand, e.g. CO
liberated in the initial synthesis [4].
‘‘gx’’ refers to the coordination mode of the phosphine–borane
fragment with the metal centre. Implicit is that the other phosphine is
always bound to the metal centre.
1
*
Corresponding author.
E-mail address: a.s.weller@bath.ac.uk (A.S. Weller).
0022-328X/$ - see front matter ꢀ 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2005.01.048

2830
N. Merle et al. / Journal of Organometallic Chemistry 690 (2005) 2829–2834
H
[M]
2. Results and discussion
H
H
H
B
H
[M]
P
H
PMe
3
[M]
B
The new, potentially chelating, phosphine borane li-
gand H2ClBÆPPh2CH2PPh2(H2ClBÆdppm) (Scheme 3)
is readily synthesised by the addition of BH2ClÆSMe2
to dppm in toluene solvent. As for addition of BH3 to
dppm, monofunctionalisation is clean, unlike that found
in other bidentate phosphines such as dppe and dppp
[7]. H2ClBÆdppm has been characterised by NMR spec-
B
B
P
H
H
Me P
H
3
PMe
H
3
A
B
C
Scheme 1.
1
troscopy and microanalysis. In the H NMR spectrum,
the BH2Cl group is observed as a quadrupolar broad-
[PF ]
[PF ]
6
6
ened, integral 2-H, quartet at d 3.93 [J(BH) 112 Hz]
1
which sharpens somewhat in the H{11B} NMR spec-
H
trum. The 31P{1H} NMR sprectum displays two reso-
nances at d 3.7 and d ꢂ27.2. The latter is a sharp
doublet [J(PP) 55 Hz] while the former is broad and is
assigned to the phosphorus atom bound to boron. The
11B NMR spectrum shows a broad resonance at d
ꢂ17.4; decoupling 1H reduces the line-width, but
31P–11B coupling is not resolved.
Ru
Ru
OC
H
H
H
H
H
Ph
Ph
P
2
P
B
B
2
P
P
Ph
Ph
2
2
(I)
(II)
Scheme 2.
Addition of H2ClBÆdppm to ½RuCpꢀðNCMeÞ ꢁ
3
½BArF4 ꢁ affords ½RuCpꢀðg2-H2ClB ꢃ dppmÞꢁ½BArF4 ꢁ, com-
pound 1, in essentially quantitative yield (Scheme 4).
Characterisation was by single crystal X-ray diffraction,
NMR spectroscopy and microanalysis. Fig. 1 shows the
solid-state structure of the cation, and Table 1 gives col-
lection and refinement data.
recently reported the synthesis, characterisation and
reactivity of some ruthenium (II) complexes ligated with
H3BÆdppm. In these complexes, the phosphine borane
can adopt either an g1 bonding mode, as in [RuCp*
(CO)(g1-H3BÆdppm)][PF6] (I), or an g2 bonding mode,
[RuCp*(g2-H3BÆdppm)][PF6] (II) (Scheme 2). Complex
II can be regarded as being ‘‘operationally unsaturated’’
in that the borane ligand can change from g2 to g1,
effectively providing a reactive 16-electron {RuCp*
(g1-H3BÆdppm)}+ fragment. Indeed, addition of carbon
monoxide to II cleanly affords I. This is similar to the
way that borohydride and allyl ligands can change their
coordination mode to reveal reactive, unsaturated, me-
tal centres [13].
The borane fragment in 1 adopts a bidentate bonding
mode, with two bridging Ru–H–B 3 centre–2 electron
interactions, very similar to that observed in the analo-
gous complex with H3BÆdppm: [RuCp*(g2-H3BÆdppm)]
[PF6] (II) [9]. The two bridging hydrogen atoms were lo-
cated and refined, and the ruthenium–borane interaction
is very similar in terms of bond lengths and angles to II.
˚
Thus the Ru–H distances in 1 [1.72(2) and 1.73(2) A] are
the same as found in II within error [1.61(4) and
We are interested in extending this chemistry of ruthe-
nium (II) fragments with chelating phosphine borane
ligands to new ligand systems; and report here the
synthesis of the new ligand H2ClBÆdppm and its
coordination with the {RuCp*}+ fragment to form ½Ru-
˚
1.70(3) A]. The Ru–B distance is slightly shorter in 1
BH Cl
2
BH Cl·SMe
2
2
Cpꢀðg2-H2ClB ꢃ dppmÞꢁ½BAr4Fꢁ ðBAr4F ¼ ½Bf3; 5-ðCF3Þ -
P
P
PPh
P
Ph
Ph
2
2
Ph
2
2
2
C6H3g ꢁꢂÞ. Preliminary reactivity studies, including
4
Scheme 3.
reaction with CO and H2/D2 are also reported.
F
F
[BAr
]
[BAr
]
4
4
H ClB·dppm
2
Ru
Ru
H
H
N
N
Cl
C
Ph
P
B
2
C
N
C
Me
Me
Me
P
Ph
2
(1)
Scheme 4.

N. Merle et al. / Journal of Organometallic Chemistry 690 (2005) 2829–2834
2831
Table 1
Crystal data and structure refinement for compound 1
Empirical formula
Formula weight
Temperature (K)
C67H51B2ClF24P2Ru
1532.16
150(2)
˚
Wavelength (A)
0.71073
Triclinic
Crystal system
Space group
ꢀ
P1
˚
a (A)
12.54200(10)
16.56200(10)
17.46200(10)
111.6770(10)
96.42
˚
b (A)
˚
c (A)
a (ꢁ)
b (ꢁ)
c (ꢁ)
93.76
3
˚
Volume (A )
3327.07(4)
2
1.529
Z
Density (calculated) (mg/cm3)
Absorption coefficient (mmꢂ1
F(000)
Crystal size (mm)
)
0.432
1540
0.50 · 0.50 · 0.45
Theta range for data collection (ꢁ) 3.29–33.19
Reflections collected
Independent reflections
Absorption correction
Data completeness
68,934
24,873 [R(int) = 0.0330]
Fig. 1. Solid-state structure of the cationic portion of complex 1.
Hydrogen atoms, apart from those associated with the borane, have
been omitted for clarity. Thermal ellipsoids are shown at the 30%
Semi-empirical from equivalents
97.6
Full-matrix least-squares on F2
24,873/0/969
1.022
˚
probability level. Selected bond lengths (A): Ru–B(1) 2.141(2), Ru–
Refinement method
P(1) 2.3043(5), Ru–H(1) 1.72(2), Ru–H(2) 1.73(2), B(1)–P(2) 1.966(2),
Cl–B(1) 1.806(1), B(1)–H(1) 1.28(2), B(1)–H(2) 1.32(3). Selected angles
(ꢁ): B(1)–Ru–P(1) 87.80(5), Cl–B(1)–P(2) 131.73(10), B(1)–H(1)–Ru
89(1), B(1)–H(2)–Ru 88(1), B(1)–Ru–H(1) 36.7(8), B(1)–Ru–H(2)
37.9(9).
Data/restraints/parameters
Goodness-of-fit on F2
Final R indices [I > 2r(I)]
R indices (all data)
R1 = 0.0447, wR2 = 0.1148
R1 = 0.0581, wR2 = 0.1260
1.722 and ꢂ1.115
3
˚
Largest diff. peak and hole (e/A )
˚
than in II [2.141(2) and 2.180(2) A, respectively]. How-
ever, both these Ru–B distances are short, being compa-
rable to that found in complexes with direct Ru–B
r-bonds [14]. Calculations on II [9] and related ruthe-
nium hydridoborates [15] do indeed indicate a small,
but significant, interaction between ruthenium and bor-
on. Both B–H bond distances are in the range expected
for a bonding B–H interaction. A significant B–H inter-
action is also indicted by the observation of B–H cou-
obvious, as compared with II (in which there are no p
interactions) the Ru–B, Ru–H and B–P bond lengths
are similar in both complexes.
In solution, the 11B{1H} NMR spectrum of 1 shows a
single resonance centred at d 28.7, showing a significant
downfield shift, Dd 46.1, compared with free ligand, in
concert with the short Ru–B distance observed in the so-
lid state. This chemical shift change is similar to that ob-
served for II compared with H3BÆdppm [Dd 55 ppm].
Similar magnitude chemical shift changes occur between
RuCp*(PMe3)(g2-H2BHCl) [19] and [PPN][BH3Cl] [22]
(Dd 52 ppm). The signal in 1 is also a doublet, showing
coupling to phosphorus [J(PB) 120 Hz], that resolves
into a doublet of triplets in the 11B NMR spectrum
[J(HB) 93 Hz]. By contrast, for the same signal in II
1
pling in the H NMR spectrum (vide infra). The B–
Ru–H angles (ꢄ37ꢁ) are as expected for a dihydridob-
orate structure rather than a boryl/metal hydride in
which these angles are substantially larger (60–80ꢁ)
˚
[16]. The B–Cl bond length in 1 [1.806(1) A] is unusually
short for four-coordinate chloroboranes, viz. 1.83–
˚
1.90 A. The two structurally characterised phophine-
mono-chloro boranes, both have significantly longer
˚
1
B–Cl bonds, viz. BH2ClÆPPh2BH2PPh2Cl, 1.877(7) A
these couplings are not resolved. The H NMR spec-
t
t
˚
[17] and Bu2-PHBH2 Bu2PÆBH2Cl, 1.898(4) A [18].
This distance in 1 is also much shorter than in the com-
trum of 1 shows Cs symmetry is present in solution, with
the methylene protons on the dppm backbone being ob-
served as an integral 2-H doublet of doublets and the
two, equivalent, bridging hydrogen atoms are observed
as a relatively well defined, but still quadrupolar broad-
ened, quartet at d ꢂ8.87 [J(BH) 93 Hz]. This is in con-
trast to II in which the B–H coupling is not resolved.
The magnitude of the 11B–1H coupling constant in the
H2ClBÆdppm ligand has been reduced by 17% [112 vs
93 Hz] on coordination to the metal fragment, consis-
tent with the description of the Ru–H–B bonding as 3
2
˚
plex RuCp*(PMe3)(g -H2BHCl), 1.862(7) A [19] which
has a similar, dihydridoborate, structure to 1. In fact,
the B–Cl bond length is more like that found in metal
complexes of three coordinate chloroboranes such as
˚
FeCp*(CO)2BClPh [1.812(12) A] [20] or FeCp(CO)2-
˚
BCl2 [1.781(3) A] [21]. As expected the 4-methylpyridine
adduct of this latter complex has a concomitantly longer
˚
B–Cl bond length [1.8853(14) A]. Whether this short B–
Cl bond length in 1 is indicative of B–Cl p overlap is not

2832
N. Merle et al. / Journal of Organometallic Chemistry 690 (2005) 2829–2834
centre–2 electron. Similar-sized decreases in the B–H
coupling constant have been noted for both mono-den-
tate and chelating phosphine boranes when coordinated
with metal fragments [4,9].
In terms of the bonding between metal and borane
fragment we have previously discussed this for II, and
concluded that is best described as a dihydridoborate
structure that has a significant Ru–B interaction [9].
The borane–metal bonding in 1 can be described in
the same way, given the similar spectroscopic and struc-
tural characteristics between II and 1.
Addition of H2 to 1 (or II) does not result in any
change in the 1H NMR spectrum either at ambient tem-
perature or low temperature (200 K), initially suggesting
no interaction of H2 with the metal centre. However,
putting 1 (or II) under an atmosphere of D2 gradually
(hours) results in the complete disappearance of the
high-field bridging hydride signals in the 1H NMR spec-
trum. At the same time the 11B NMR spectrum of 1
changes from a doublet of triplets to a doublet at essen-
tially the same chemical shift, indicating substitution of
H for D. The B–D coupling, which would be signifi-
cantly smaller (ꢄ6 times) than the B-H coupling, is
not resolved. The 31P{1H} NMR spectrum remains un-
changed on treatment with D2. This data show that H/D
exchange is occurring in solution to afford ½RuCpꢀ
We have previously shown that the borane fragment
in II can move from g2 to g1, allowing two electron li-
gands to coordinate, such as MeCN, CO or PMe3 [9].
This change in bonding of the borane effectively makes
the metal centre ‘‘operationally unsaturated’’, revealing
a latent 16-electron metal fragment. Similar reactivity
is observed for 1. Addition of CO affords ½RuCpꢀ-
ðCOÞðg1-H2ClB ꢃ dppmÞꢁ½BArF4 ꢁ (2), which has been
characterised spectroscopically by analogy with [RuCp*-
(CO)(g1-H3BÆdppm)][PF6] [9] (Scheme 5). In solution a
quadrupolar broadened, high field signal is observed in
ðg2-D2ClB ꢃ dppmÞꢁ½BArFꢁ, 1-d2 (Scheme 6). In the H
2
4
NMR spectrum a single high-field resoance is observed
at essentially the same chemical shift [d ꢂ8.85] as found
for 1. Complete deuteration also occurs for II to afford
II-d3.
H/D exchange in phosphine boranes has previously
been observed in the Re(PPh3)2H7/H3BÆPMe3 system
when heated in C6D6 [23]. A mechanism that involves
deuteration of a {Re(PPh3)2H5} metal fragment by
C6D6 followed by the coordination of H3BÆPMe3 and
scrambling of hydrido and deuterio ligands has been
described. No metal–borane intermediates, such as
Re(PPh3)2D5(g1-H3BÆPMe3), were observed however.
A similar mechanism can be used to account for the
H/D exchange observed in 1 and II, however in this case
the metal–borane complex is well characterised (Scheme
7). D2 oxidatively adds to the Ru(II) centre in 1, presum-
ably initially through a dihydrogen adduct with a g1-
borane ligand. Oxidative addition of H2 to ruthenium
(II) cyclopentadienyl phosphine complexes is known to
1
the H NMR spectrum at d ꢂ9.47, of integral 1-H rela-
tive to the Cp* resonance. This is assigned to the bridging
Ru–H–B hydrogen. The methylene protons are now ob-
served as two multiplets (d of d of d) showing that the Cs
symmetry present in 1 has been lost on CO coordination.
1
In the H{11B} NMR spectrum the high field resonance
sharpens and a new integral 1-H peak at d 1.85 appears.
We assign this to the terminal B–H. The observation of
both terminal and bridging B–H in the room tempera-
ture NMR spectrum shows that they do not exchange
on the NMR timescale. This is in contrast to I, in which
rapid exchange of these groups occurs at room tempera-
ture. In the 31P{1H} NMR spectrum a sharp signal at d
50.0 and a broad signal at d 6.0 are observed, the latter
assigned to the boron-bound phosphorus atom. In the
11B NMR spectrum a broad signal is observed at d
ꢂ18.2 ppm, this being very similar to free ligand. This
resonance is shifted 47 ppm upfield compared with 1,
demonstrating the structural change from g2 to g1 on
reaction with CO. The IR spectrum shows a single CO
stretching band at 1908 cmꢂ1 which is found to higher
frequency than that for [RuCp*(CO)(g1-H3BÆdppm)]
[PF6] (I) (1963 cmꢂ1) [9].
form dihydride complexes such as ½RuCpꢀH2ðPiPr3Þ ꢁ
2
½BArF4 ꢁ [24]. Breaking a B–H bond and making a B–D
bond (similar to the exchange process observed in boro-
hydride complexes such as OsH3(g2-BH4)(PR3)2 [25]) ef-
fects H/D exchange. Reductive elimination of HD(g)
would then afford (initially partially) deuterated 1.
Experimentally, HD is observed [d 4.55, J(DH) 43 Hz]
1
in the H NMR spectrum of 1 under a D2 atmosphere
after 15 min. Consistent with this proposed mechanism,
compound 2 is unchanged on exposure to D2 as it is
F
[BAr
]
4
[PF ]
6
F
F
[BAr
]
4
[BAr
]
4
Ru
Ru
D
D
CO
D
D
Ru
Cl
OC
Ph
D
Ru
H
Ph
2
P
H
B
Ph
2
P
B
H
Cl
H
Cl
P
B
2
Ph
2
P
B
P
P
Ph
2
P
Ph
2
P
Ph
2
Ph
2
(1-d )
(II-d )
2
(2)
3
Scheme 5.
Scheme 6.

N. Merle et al. / Journal of Organometallic Chemistry 690 (2005) 2829–2834
2833
+D
-D
- HD
2
Ru
Ru
Ru
H
Ru
D
H
D
H
H
Cl
P
Cl
H
Cl
P
Ph
2
Cl
H
Ph
Ph
D
D
P
B
B
H
Ph
P
2
2
2
B
B
D
2
P
P
P
P
Ph
2
Ph
Ph
Ph
2
2
2
Scheme 7.
unable to generate an unsaturated species, which also
has a coordinated borane – both being necessary for
H/D exchange to occur. An alternative mechanism that
involves initial oxidative addition of B–H to the metal
(followed by H/D exchange with D2) has been dis-
counted for related systems by Shimoi due to the high
energy of the B–H r* orbital that would necessarily be
involved in such a process [23,26]. Oxidative addition
of three coordinate boranes to low valent transition me-
tal centres is known [27].
those associated with the borane which were located in
the final difference map and refined without constraints.
Crystallographic data files have been deposited with the
Cambridge Crystallographic Data Centre (CCDC
255156), 12 Union Road, Cambridge CB2 1EZ (UK);
Tel.: +44 1223 336 408, fax: +44 1223 336 033, e-mail:
deposit@ccdc.cam.ac.uk.
3.4. Synthesis
3.4.1. H2ClBÆdppm
Me2SÆBH2Cl (0.115 g, 1.04 mmol) was added to a
toluene solution of dppm (0.400 g, 1.04 mmol) and stir-
red for 1 h. Solvent was reduced in vacuo to minimum
volume and layered with hexane. Storage at ꢂ30 ꢁC over
3 days affords colourless crystalline material. Mass
0.355 g, yield 82%. C25H24BClP2 requires C, 69.40; H,
5.59. Found: C, 68.9; H, 5.72%. NMR data (all in
C6D6) d(1H): 8.32–6.86 (20H, m, Ph), 3.93 [2H, br q,
3. Experimental
3.1. General
All manipulations were carried out under an atmo-
sphere of argon using standard Schlenk-line and glove-
box techniques. Glasswares were predried in an oven
at 130 ꢁC and flamed with a blow-torch under vacuum
prior to use. CH2Cl2 and pentane were distilled from
CaH2. CD2Cl2 was dried over CaH2 and distilled under
BH , J(BH) 112 Hz], 3.18 [2H, d, JðP
HÞ 10.5 Hz,
ðBH3Þ
2
CH2]. d(1H{11B}) (selected): 3.93 (2H, br s, BH2).
d(31P{1H}): 3.7 (1P, br, P–B), ꢂ27.2 [1P, d, PPh2,
J(PP) 55 Hz]. d(11B{1H}): ꢂ17.4 (1B, br s, BH2Cl).
vacuum. ½RuCpꢀðNCMeÞ ꢁ½BArF4 ꢁ was prepared by salt
3
metathesis of [RuCp*(NCMe)3][PF6] [28] with K½BArFꢁ
4
[29]. Microanalyses were performed by Mr. Alan Carver
(University of Bath microanalytical service).
3.4.2. RuCpꢀ g2-H2ClB ꢃ dppm BArF4
1
½RuCpꢀðMeCNÞ ꢁ½BArF4 ꢁ (0.150 g, 0.122 mmol) and
3
H2ClBÆdppm (0.053 g, 0.122 mmol) were stirred in
20 cm3 of CH2Cl2 for 30 min at room temperature.
The solvent was removed in vacuo to leave red oil. Crys-
tals suitable for an X-ray diffraction study were grown
by dissolving the oil in minimum CH2Cl2 and layering
with pentane to yield red–orange crystals. Mass
0.177 g, yield 95%. C67H51B2ClF24P2Ru requires C,
52.52; H, 3.35%. Found: C, 52.70; H, 3.39%. NMR data
3.2. NMR spectroscopy
1
1H, H{11B}, 11B, 11B{1H} and 31P{1H} NMR spec-
tra were recorded on Bruker Avance 300 or 400 MHz
spectrometers. Residual protio solvent was used as refer-
ence for 1H and 2H NMR spectroscopy (CH2Cl2
d = 5.32, CD2Cl2 d = 5.30). 11B and 31P were referenced
to external BF3 ÆOEt2 and 85% H3PO4, respectively. Val-
ues are quoted in ppm. Coupling constants are given in
Hertz. 31P–1H coupling constants were deduced from
1H{31P-selective} experiments.
(all in CD2Cl2) d(1H): 7.86–7.20 (32H, m, Ph þ BArF),
4
2.96 [2H, dd, CH, J(PH), 8.8 Hz, JðP
HÞ 12.1 Hz],
ðBH3Þ
1.62 (15H, s, Me), ꢂ8.87 [2H, br q, BH2, J(BH)
92.5 Hz]. d(1H{11B}) (selected): ꢂ8.87 (2H, br s, BH2).
d(31P{1H}): 64.2 [1P, d, PPh2, Hz, J(PP) 83.3 Hz], 13.4
(1P, br, P–B). d(11B): 28.7 [1B, dt, BH2Cl, J(PB)
120 Hz, J(HB) 93 Hz]. d(11B{1H}): 28.7 [1B, d, BH2Cl,
J(PB) 120 Hz], ꢂ6.6 (1B, s, BArF4 ). d(2H): ꢂ8.85.
3.3. X-ray crystallography
The crystal structure data for 1 were collected on a
Nonius-Kappa CCD diffractometer with details pro-
vided in Table 1. Structure solution, followed by full-
matrix least-squares refinement was performed using
the SHELXL suite of programs throughout [30]. Hydrogen
atoms were included in calculated positions apart from
3.4.3. RuCp CO g2-H2ClB ꢃ dppm BArF4
2
A CH2Cl2 solution of ½RuCpꢀðg2-H2ClB ꢃ dppmÞꢁ-
½BArF4 ꢁ (0.100 g, 0.128 mmol) was stirred for 15 min un-
der a CO atmosphere to give a yellow solution. Solvent

2834
N. Merle et al. / Journal of Organometallic Chemistry 690 (2005) 2829–2834
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[11] M. Shimoi, K. Katoh, H. Ogino, J. Chem. Soc., Chem. Commun.
(1990) 811.
was removed in vacuo to leave a yellow solid.
C68H51B2ClF24OP2Ru requires C, 52.35; H, 3.29%.
Found: C, 52.1; H, 4.01%. NMR data (all in CD2Cl2)
d(1H{11B}): 7.75–6.97 (32H, m, Ph þ BArF4 ), 3.61 [1H,
[12] M. Shimoi, K. Katoh, H. Tobita, H. Ogino, Inorg. Chem. 29
(1990) 814.
ddd, CH, J(PH) 10.9 Hz, JðP
HÞ 10.9 Hz, J(HH)
ðBH3Þ
[13] T.J. Marks, J.R. Kolb, Chem. Rev. 77 (1977) 263.
[14] T. Yasue, Y. Kawano, M. Shimoi, Chem. Lett. (2000) 58;
C.E.F. Rickard, W.R. Roper, A. Williamson, L.J. Wright,
Organometallics 19 (2000) 4344.
15.5 Hz], 3.30 [1H, ddd, CH, J(PH) 7.7 Hz, JðP
HÞ
ðBH3Þ
14.7 Hz, J(HH), 15.5 Hz], 1.85 (1H, br m, BH), 1.65
[15H, d, Me, J(PH), 2.0 Hz], ꢂ9.47 [1H, br s, BH3].
d(31P{1H}): 50.0 [1P, d, PPh2, J(PP) 44.8 Hz], 6.0 (1P,
br, P–B). d(11B{1H}): ꢂ5.9 (1B, s, BArF4 ), ꢂ18.2 (1B,
br). IR (KBr), m cmꢂ1: 1980 (m, CO).
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Dalton Trans. (1978) 40.
The Royal Society and the EPSRC (GR/R90475/01)
for support. Dr. John Lowe for assistance with record-
2
ing the H NMR spectra.
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