Alkenyl and alkynyl complexes of osmium(II) derived from [OsH(Cl)(CO)(BTD)(PPh3)2] (BTD = 2,1,3-benzothiadiazole)

Article abstract of DOI:10.1039/a805303k

Treatment of [OsH(CA)(NCMe)₂(PPh₃)₂]⁺ (A = O or S) with [NEt₄]Cl and 2,1,3-benzothiadiazole (BTD) provided [OsH(Cl)(CA)(BTD)(PPh₃)₂] (A = O or S). Under mild conditions, the complex [OsH(Cl)(CO)(BTD)(PPh₃)₂] hydro-osmiates ethynyltoluene, ethyne and di(4-tolyl)butadiyne to provide vinyl complexes [Os(CH=CHR)Cl(CO)(BTD)-(PPh₃)₂] (R = C₆H₄Me-4), [Os(CH=CH₂)Cl(CO)(BTD)(PPh₃)₂] and [Os{C(C≡CR)≡CHR}Cl(CO)(BTD)(PPh₃)₂]. Complex [OsH(CO)(NCMe)₂(PPh₃)₂]⁺ reacted with HC≡CR to provide [Os(CH=CHR)(CO)(NCMe)₂(PPh₃)₂]⁺ which is converted by [NEt₄]Cl into [Os(CH=CHR)Cl(CO)(NCMe)(PPh₃)₂]. Treatment of [Os(CH=CHR)Cl(CO)-(BTD)(PPh₃)₂] with CNCMe₃ or CO provided [Os(CH=CHR)Cl(CO)(L)(PPh₃)₂] (L = CNCMe₃ or CO). The dithiocarbamate complex [Os(CH=CHR)(S₂CNMe₂)(CO)(PPh₃)₂] and the osmatetraborane [Os(CH=CHR)-(B₃H₈)(CO)(PPh₃)₂] resulted from the reactions of [Os(CH=CHR)Cl(CO)(BTD)(PPh₃)₂] with Na[S₂CNMe₂] and [NBu_n4][B₃H₈], respectively, whereas with K[HB(pz)₃] (pz = pyrazolyl) initially [Os(CH=CHR)(CO)(PPh₃)₂-{η²-HB(pz) ₃}] was formed which is converted into [Os(CH=CHR)(CO)(PPh₃){HB(pz)₃}] on heating. No intermediates are however observed in the corresponding reaction with 1,4,7-trithiacyclononane ([9]aneS₃) to provide [Os(CH=CHR)(CO)(PPh₃)([9]aneS₃)]⁺. The alkynyl complex [Os(C≡CR)Cl(CO)(BTD)(PPh₃)₂] was obtained from either (i) the reaction of [OsH(Cl)(CO)(BTD)(PPh₃)₂] with [Hg(C≡CR)₂] or (ii) [Os(CH=CHR)Cl(CO)(BTD)(PPh₃)₂] with an excess of HC≡CR. Treatment of [Os(C≡CR)Cl(CO)(BTD)(PPh₃)₂] with Na[S₂CNMe₂] or alternatively [Os(CH=CHR)(S₂CNMe₂)(CO)(PPh₃)₂] with an excess of HC≡CR provided [Os(C≡CR)(S₂CNMe₂)(CO)(PPh₃) ₂], which can also be obtained from [OsH(S₂CNMe₂)(CO)(PPh₃)₂] and [Hg(C≡CR)₂]. The BTD in [Os(OCR)Cl(CO)-(BTD)(PPh₃)₂] is substituted by CNCMe₃ to provide [Os(C≡CR)Cl(CO)(CNCMe₃)(PPh₃)₂]. The reaction of [OsH(Cl)(CS)(BTD)(PPh₃)₂] with HC≡CR provided [Os(CH=CHR)Cl(CS)(BTD)(PPh₃)₂] which in contrast to [Os(CH=CHR)Cl(CO)(BTD)(PPh₃)₂] reacts with carbon monoxide to provide the thiocinnamoyl complex [Os(η²-SCCH=CHR)Cl(CO)(PPh₃)₂].

Full text of DOI:10.1039/a805303k

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Alkenyl and alkynyl complexes of osmium(II) derived from
[OsH(Cl)(CO)(BTD)(PPh3)2] (BTD ؍ 2,1,3-benzothiadiazole)
Anthony F. Hill* and James D. E. T. Wilton-Ely
Centre for Chemical Synthesis, Department of Chemistry, Imperial College of Science,
Technology and Medicine, South Kensington, London, UK SW7 2AY. E-mail: a.hill@ic.ac.uk
Received 8th July 1998, Accepted 17th August 1998
Treatment of [OsH(CA)(NCMe)2(PPh3)2]ϩ (A = O or S) with [NEt4]Cl and 2,1,3-benzothiadiazole (BTD) provided
[OsH(Cl)(CA)(BTD)(PPh3)2] (A = O or S). Under mild conditions, the complex [OsH(Cl)(CO)(BTD)(PPh3)2] hydro-
osmiates ethynyltoluene, ethyne and di(4-tolyl)butadiyne to provide vinyl complexes [Os(CH᎐CHR)Cl(CO)(BTD)-
᎐
᎐
(PPh ) ] (R = C H Me-4), [Os(CH᎐CH )Cl(CO)(BTD)(PPh ) ] and [Os{C(C᎐CR)᎐CHR}Cl(CO)(BTD)(PPh ) ].
Complex [OsH(CO)(NCMe) (PPh ) ] reacted with HC᎐CR to provide [Os(CH᎐CHR)(CO)(NCMe) (PPh ) ]
᎐
᎐
᎐
3
2
6
4
2
3
2
3
2
ϩ
ϩ
᎐
᎐
᎐
2
3
2
2
3 2
which is converted by [NEt ]Cl into [Os(CH᎐CHR)Cl(CO)(NCMe)(PPh ) ]. Treatment of [Os(CH᎐CHR)Cl(CO)-
᎐
᎐
4
3 2
(BTD)(PPh ) ] with CNCMe or CO provided [Os(CH᎐CHR)Cl(CO)(L)(PPh ) ] (L = CNCMe or CO). The
᎐
3
2
3
3
2
3
dithiocarbamate complex [Os(CH᎐CHR)(S CNMe )(CO)(PPh ) ] and the osmatetraborane [Os(CH᎐CHR)-
᎐
᎐
2
2
3 2
(B H )(CO)(PPh ) ] resulted from the reactions of [Os(CH᎐CHR)Cl(CO)(BTD)(PPh ) ] with Na[S CNMe ]
᎐
3
8
3
2
3
2
2
2
and [NBun ][B H ], respectively, whereas with K[HB(pz) ] (pz = pyrazolyl) initially [Os(CH᎐CHR)(CO)(PPh ) -
᎐
4
3
8
3
3 2
{η2-HB(pz) }] was formed which is converted into [Os(CH᎐CHR)(CO)(PPh ){HB(pz) }] on heating. No inter-
᎐
3
3
3
mediates are however observed in the corresponding reaction with 1,4,7-trithiacyclononane ([9]aneS3) to provide
ϩ
᎐
[Os(CH᎐CHR)(CO)(PPh )([9]aneS )] . The alkynyl complex [Os(C᎐CR)Cl(CO)(BTD)(PPh ) ] was obtained from
᎐
᎐
3
3
3 2
᎐
either (i) the reaction of [OsH(Cl)(CO)(BTD)(PPh ) ] with [Hg(C᎐CR) ] or (ii) [Os(CH᎐CHR)Cl(CO)(BTD)(PPh ) ]
with an excess of HC᎐CR. Treatment of [Os(C᎐CR)Cl(CO)(BTD)(PPh ) ] with Na[S CNMe ] or alternatively
᎐
᎐
3
2
2
3 2
᎐
᎐
᎐
᎐
3
2
2
2
᎐
᎐
[Os(CH᎐CHR)(S CNMe )(CO)(PPh ) ] with an excess of HC᎐CR provided [Os(C᎐CR)(S CNMe )(CO)(PPh ) ],
᎐
᎐
᎐
2
2
3
2
2
2
3 2
᎐
᎐
which can also be obtained from [OsH(S CNMe )(CO)(PPh ) ] and [Hg(C᎐CR) ]. The BTD in [Os(C᎐CR)Cl(CO)-
᎐
᎐
2
2
3
2
2
᎐
(BTD)(PPh ) ] is substituted by CNCMe to provide [Os(C᎐CR)Cl(CO)(CNCMe )(PPh ) ]. The reaction of
᎐
3
2
3
3
3 2
᎐
[OsH(Cl)(CS)(BTD)(PPh ) ] with HC᎐CR provided [Os(CH᎐CHR)Cl(CS)(BTD)(PPh ) ] which in contrast
᎐
᎐
3
2
3 2
to [Os(CH᎐CHR)Cl(CO)(BTD)(PPh ) ] reacts with carbon monoxide to provide the thiocinnamoyl complex
᎐
3
2
[Os(η2-SCCH᎐CHR)Cl(CO)(PPh ) ].
᎐
3
2
Introduction
PPh3
M
PPh3
OC
H
AC
H
Cl
PPh3
Cl
The hydrometallation of alkynes by hydrido complexes of
osmium and ruthenium provides a facile entry into the chem-
istry of σ-vinyl complexes.1 The readily accessible complex
[RuH(Cl)(CO)(PPh3)3] 1a2 has been shown to react with
alkynes3,4 and diynes5 to provide co-ordinatively unsaturated
σ-vinyl or σ-enynyl complexes which are themselves valuable
precursors to a wide range of complexes bearing isocyanide,6,7
poly(azolyl)borate,8 triboronate,9 and trithiacyclononane,10
dithiocarbamate,11 carboxylate12 and phosphoniodithiocarb-
oxylate13 coligands. For many of these compounds the
M
L
PPh3
PPh3
M = Ru 1a
M = Os 1b
M = Ru, A = O, L = BTD 2a
M = Ru, A = O, L = BSD 2b
M = Os, A = O, L = BTD 2c
M = Os, A = S, L = BTD 2d
Hβ
Hα
N
N
Cα Cβ
E
co-ordinatively saturated adducts [Ru(CH᎐CHR)Cl(CO)(L)-
᎐
(PPh3)2] [L = 2,1,3-benzothiadiazole (BTD) or 2,1,3-benzo-
selenadiazole (BSD)] serve equally well as precursors by virtue
of the lability of the heterocyclic ligands. These vinyl complexes
result under mild conditions from the reactions of the hydrido
complexes [RuH(Cl)(CO)(L)(PPh3)2] (L = BTD 2a or BSD
2b)14 with alkynes and alkynols.15 Esteruelas, Oro and Werner16
have developed an enormously rich chemistry based on the
related complexes [MH(Cl)(CO)(PPri3)2] (M = Ru or Os)16
which are stable and highly reactive 16-electron species due to
the steric encumbrance of the PPri3 ligands which precludes the
formation of tris(phosphine) complexes in contrast to the PPh3
relatives. Whilst the PPri3 class of complex allows the study of
osmium σ-vinyl chemistry in parallel with that of ruthenium,
the hydrometallation of alkynes by [OsH(Cl)(CO)(PPh3)3] 1b
has met with very limited success. Roper and co-workers17 have
LnOs
Hβ′
E = S (BTD)
E = Se (BSD)
described an unusual cyclotrimerisation process which occurs
with ethyne, the initial stages of which are consistent with
the intermediate formation of [Os(CH᎐CH )Cl(CO)(PPh ) ].
However, in general it appears in the equilibrium reaction
with alkynes that the hydride precursor is preferred to the
alkyne insertion product, in distinct contrast to the chemistry
of ruthenium. This interpretation follows from two observ-
᎐
2
3 2
ations (Scheme 1): whilst the complex [Ru(CH᎐CHPh)Cl-
᎐
(CO)(PPh3)2] may be obtained from the reaction of 1a with
either ethynylbenzene3 or [Hg(CH᎐CHPh) ],18 there is no
᎐
2
apparent reaction between the osmium analogue 1b and
J. Chem. Soc., Dalton Trans., 1998, 3501–3510
3501

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[Hg(CH=CHPh)2]
(Ref. 20)
L
Os
L
H
R
L H
R
C
H
MeCN
MeCN
Cl
L
Ru
L
L
C
CO
C
(i)
C
CO
Ph
H
H
Os
H
OC
H
L
OC
C
C
MeCN
Ru
L
H-C≡C-Ph
(Ref. 3)
L
Cl
Cl
5+
6
1a
(ii)
(iii)
L
OC
H
L
Os
L
Hg(CH=CHPh)2
H-C≡C-Ph
Cl
R
C
L
Os
L
L
H
MeCN
MeCN
Cl
H
CO
C
1b
Os
L
CO
H
Me3CNC
[Catalyst]
3a+
7a
L
"
"
OC
H
Os C
C
H2C=CHPh
+ Hg0
Cl
Ph
(i), (v)
(iv)
(iii)
H
L
(not isolated)
R
L
H
L
Cl
BTD
Cl
2c
C
CO
C
H
CO
(ii)
L
Os
L
Os
L
(C≡C-Ph)2
H
BTD
Hg(C≡CPh)2
OC
L
Os
L
4a
H
Cl
1b
(vi)
[Catalyst]
(vii)
Ph
L
Hg0
OC
Cl
C
H
R
R
Os
L
C
C
L
Os
L
L
Os
L
H
C Ph
Cl
BTD
4c
Cl
OC
C
CO
C
CO
C
H
C
C
H
R
(not isolated)
7b
Scheme 1 L = PPh3.
᎐
Scheme 2 L = PPh3, R = C6H4Me-4. Reagents: (i) [Et4N]Cl; (ii) HC᎐
CR; (iii) CNCMe3; (iv) MeCN; (v) BTD; (vi) RC᎐C᎐C᎐CR; (vii) CO.
᎐
᎐
᎐
᎐
᎐
ethynylbenzene. Furthermore, with [Hg(CH᎐CHPh) ] catalytic
᎐
2
demercuriation occurs to regenerate 1b, elemental mercury, and
presumably styrene and ethynylbenzene. This is consistent with
high yields of the desired complex 2c. This complex may be
assumed on the basis of spectroscopic data to adopt the stereo-
chemistry shown in Scheme 2, which has been previously estab-
lished for the ruthenium analogue 2a.14 Thus the hydride ligand
gives rise to a triplet resonance at δ Ϫ15.00 [J(PH) = 16.2 Hz] in
the formation of [Os(CH᎐CHPh)Cl(CO)(PPh ) ] which under
᎐
3
2
the reaction conditions (refluxing toluene) and in the presence
of liberated PPh3 undergoes β-Os–H elimination to generate
ethynylbenzene and 1b.18 The second illustration comes from
1
᎐
the reactions of 1 with [Hg(C᎐CPh) ]: in the case of ruthenium
the H NMR spectrum, confirming that it is cis to two chem-
᎐
2
᎐
(1a) the product is the enynyl complex [Ru{C(C᎐CPh)᎐CHPh}-
ically equivalent phosphine ligands. Intense ν(OsH) and ν(CO)
absorptions are visible in the solid state infrared spectrum
(Nujol) at 1974 and 1905 cmϪ1, respectively. The molecular
composition is supported by positive ion FAB mass spectro-
scopy which displays no molecular ion but instead a [M Ϫ
BTD]ϩ fragment at m/z = 780. Facile loss of the BSD ligand in
the FAB mass spectra is a common feature of BSD com-
plexes.14,15,24 Fragmentations are however also observed which
involve retention of the BTD ligand, thereby confirming that
it is co-ordinated in the complex.
᎐
᎐
Cl(CO)(PPh3)2]19 which is also obtained from the reaction
of 1a with diphenylbutadiyne.5 This complex catalyses the
᎐
demercuriation of [Hg(C᎐CPh) ] to provide elemental mercury
᎐
2
and diphenylbutadiyne and may be recovered after the catalysis.
Although 1b will also catalyse this demercuriation, the organo-
metallic product obtained after catalysis is the starting hydride
complex 1b, rather than an enynyl derivative (Scheme 1).20
The complex [OsH(O2CCF3)(CO)(PPh3)2] has been shown
᎐
to react with tolane (PhC᎐CPh) to provide the cis-stilbenyl
᎐
complex [Os(CPh᎐CHPh)(O CCF )(CO)(PPh ) ].21,22 This
᎐
2
3
3 2
result, taken in combination with the above considerations, led
us to conclude that the hiatus in the potential alkyne hydro-
metallation chemistry based on 1b lies in (i) the competitive co-
ordination of the third phosphine ligand and (ii) the inherent
stability of 1b relative to alkyne insertion products. We have
therefore investigated the synthesis of the BTD complex [OsH-
(Cl)(CO)(BTD)(PPh3)2] 2c, and now show that a rich organo-
metallic chemistry is indeed accessible from this species.
Alkenyl complexes
An instant deep purple coloration is observed on addition of
4-ethynyltoluene to a solution of complex 2c in dichloro-
methane. A complex formulated as [Os(CH᎐CHC H Me-4)-
Cl(CO)(BTD)(PPh3)2] 4a may be isolated in high yield on addi-
tion of ethanol. No ν(OsH) absorption is observed in the
infrared spectrum (Nujol), only an intense ν(CO) absorption at
1899 cmϪ1. The species formed is confirmed as a vinyl complex
᎐
6
4
1
from the characteristic resonances exhibited in the H NMR
Results and discussion
spectrum: a doublet of triplets is observed for the vinylic
α-proton to low field at δ 9.08 [J(HαHβ) = 17.2, J(HαP) = 2.6 Hz]
showing typical coupling to two mutually trans phosphines.
The comparatively low field chemical shift for this resonance is
consistent with the vinyl ligand being co-ordinated trans to a
good donor ligand. The β-proton of the vinyl ligand gives rise
to a doublet resonance at δ 5.87. An (AB)2 system is observed
for the tolyl substituent [δ 6.84, 6.97; J(AB) = 7.9 Hz] as well as
a singlet resonance at δ 3.03 due to the methyl group. The pres-
ence of the BTD ligand is betrayed only by the microanalytical
Our initial attempt to prepare [OsH(Cl)(CO)(BTD)(PPh3)2] 2c
in a manner analogous to the ruthenium example (2a) failed.
Thus heating complex 1b with an excess of BTD in refluxing
tetrahydrofuran fails to provide pure 2c. Rather, essentially
independent of reaction duration, an equilibrium mixture of
colourless 1b and orange 2c is obtained, further supporting
the idea that phosphine competes effectively for co-ordination
to osmium. An alternative approach was therefore developed to
remove this competition. The salt [OsH(CO)(NCMe)2(PPh3)2]-
ClO4 3aؒClO4 is readily obtained via the reaction of 1b with
AgClO4ؒH2O in refluxing acetonitrile.23 Heating 3aؒClO4 in
refluxing ethanol with an excess of [NEt4]Cl and BTD provides
1
data since IR absorbances for it are typically weak and the H
NMR resonances are obscured by the phosphine resonances.
The complex is thus as formulated and this is supported by
3502
J. Chem. Soc., Dalton Trans., 1998, 3501–3510

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FAB MS data, and subsequent derived chemistry. In a similar
in the FAB mass spectrum at m/z = 896. As with 4, the stereo-
manner, the red parent vinyl analogue [Os(CH᎐CH )Cl(CO)-
chemistry does not follow definitely from spectroscopic data,
however the trans influence of the σ-organyl ligand may be
expected to favour a vacant co-ordination site to this ligand
prior to isocyanide co-ordination. In a similar manner, treating
4a with carbon monoxide (1 atmosphere) leads to decoloris-
ation and formation of the cis-dicarbonyl complex 7b. In this
case the stereochemistry at osmium is unambiguous, given the
appearance of two ν(CO) IR absorptions [CH2Cl2, 2021, 1953
cmϪ1] and a singlet 31P-{1H} NMR resonance (δ Ϫ6.45).
᎐
2
(BTD)(PPh3)2] 4b can also be prepared from 2c and ethyne at
ambient temperature and pressure. The 1H NMR spectrum
is more complex than that of 4a, with the α-proton resonating
as a low field multiplet at δ 8.57. The β- and βЈ-protons are
observed at
δ 4.88 [d, J(HαHβ) = 17.6] and 5.96 [dd,
J(HαHβЈ) = 10.6, J(HβHβЈ) = 2.2 Hz], respectively. Perhaps sur-
prisingly, the species 4b can also be prepared from a mixture of
1b and BTD in solution on exposure to a stream of acetylene.
This is however not the case with any of the other vinyl com-
Treatment of complex 4a with an ethanolic solution of
Na[S2CNMe2]ؒ2H2O results in a yellow solution from which the
᎐
plexes discussed here. The purple enynyl complex [Os{C(C᎐C-
᎐
C H Me-4)᎐CHC H Me-4}Cl(CO)(BTD)(PPh ) ] 4c is readily
pale yellow complex [Os(CH᎐CHC H Me-4)(S CNMe )(CO)-
᎐
6 4 2 2
(PPh3)2] 8 can be isolated in high yield (88%) (Scheme 3). The
᎐
6
4
6
4
3
2
obtained from 2c by the same route employing the diyne
᎐
(C᎐CC H Me-4) , which is itself obtained from a metal-
᎐
6
4
2
25
᎐
mediated demercuriation of [Hg(C᎐CC H Me-4) ]. Spectro-
᎐
6
4
2
H
pz
scopic data are essentially similar to those of the species
described above with the exceptions of (i) the vinylic proton
which was found to resonate as a broad singlet at δ 6.43 in the
B
H
B
N
N
N
N
N
N
Heat
N
N
N
1
᎐
N
H NMR spectrum, and (ii) the weak ν(C᎐C) IR absorption due
᎐
L
Os
H
R
to the free alkynyl group (Nujol: 2158, 2136 cmϪ1). The stereo-
chemistry of the equatorial plane of the complexes 4 does not
follow unambiguously from spectroscopic data, however the
Ph3P
C
C
C
Os
H
R
H
H
L
C
C
C
O
11b
H
C
O
10b
geometry of the 16-electron complexes [Ru(CPh᎐CHPh)Cl-
᎐
S
R
H
(CO)(PPh3)2],3 [Ru(C6H4Me-4)Cl(CO)(PPh3)2],18 [Ru(C6H4Me-
S
C
CO
(i)
H
2)Cl(CO)(PPh3)2]18 and [Ru(CH᎐CHCH PPh )Br(CO)(PPh ) ]-
(ii)
Os
L
᎐
2
3
3 2
S
4
PF6 approaches square-based pyramidal with the σ-organyl
ligand occupying an apical site trans to the vacant co-ordin-
ation site. It is therefore reasonable that the labile BTD ligand
co-ordinates in this site.
12a+
R
C
L
Cl
C
(iii)
H
Os
H
B
H
BTD
CO
H
H
L
R
H
H
H
H
L
B
C
CO
C
4a
Os
The complex 3aϩ itself provided a useful entry point into
further osmium(II) σ-vinyl chemistry: the pale-brown vinyl salt
B
H
H
L
(iv)
[Os(CH᎐CHC H Me-4)(CO)(NCMe) (PPh ) ]ClO 5ؒClO4 is
9
᎐
6
4
2
3
2
4
(vi)
H
2c
obtained on stirring with an excess of 4-ethynyltoluene for 3 h
1
(v)
at room temperature. Singlet resonances are visible in the H
NMR spectrum at δ 1.74 and 1.85 for the two chemically dis-
tinct and mutually cis co-ordinated acetonitrile ligands. The
facile loss of the nitrile ligands is a feature of the FAB mass
spectrum with isotopic envelopes being observed at m/z = 902
for [M Ϫ MeCN]ϩ and 859 for [M Ϫ 2MeCN]ϩ, in addition to
a molecular ion observed at m/z = 945. One acetonitrile ligand
in the complex 5ϩ is labile: thus treating 5ؒClO4 with [NEt4]Cl
L
L
R
R
C
S
Cl
BTD
C
CO
C
C
CO
Me2N
C
Os
L
Os
L
S
H
8
13
(iv)
(vii)
(vi)
R
R
L
L
Os
L
provides the complex [Os(CH᎐CHC H Me-4)Cl(CO)(NCMe)-
᎐
6
4
C
C
S
Cl
C
CO
C
Me2N
C
(PPh3)2] 6. Spectroscopic data for this complex are identical to
those for the complex obtained from the reaction of 4a with
acetonitrile. This is perhaps surprising since the nitrile in 5ϩ
which is trans to the vinyl ligand might have been expected to be
the more labile of the two. Such a regioselective substitution is
reminiscent of the carbonylation of the complex [RuH(CO)-
(NCMe)2(PPh3)2]ClO4 which proceeds under ambient condi-
tions to provide cct-[RuH(CO)2(NCMe)(PPh3)2]ClO4 and only
under higher pressures and temperatures to mer-trans-
[RuH(CO)3(PPh3)2]ClO4.23,26
The BTD ligand of complex 4a is labile, as had been demon-
strated for the related σ-aryl complex [Os(C6H4Me-4)Cl(CO)-
(BTD)(PPh3)2]:24 addition of an excess of pivaloisocyanide
(CNCMe3) to 4a leads to instant decolorisation of the purple
Os
L
S
Me3CNC
CO
14
15
(v)
[OsH(S2CNMe2)(CO)L2]
Scheme 3 L = PPh3, R = C6H4Me-4. Reagents: (i) K[HB(pz)3]; (ii)
[9]aneS3; (iii) [Bu N][B3H8]; (iv) HC᎐CR, heat; (v) [Hg(C᎐CR)2];
(vi) Na[S2CNMe2]ؒ2H2O; (vii) CNCMe3.
n
᎐
᎐
4
᎐
᎐
methyl groups of the dithiocarbamate ligand give rise to two
singlet resonances at δ 2.31 and 2.58, to slightly higher field
than the tolyl methyl singlet at δ 2.20. The protons of the vinyl
and the aromatic protons of the tolyl group also give rise to
characteristic features. New bands of medium intensity and
characteristic of the dithiocarbamate ligand were observed in
the ‘fingerprint’ region of the infrared spectrum (Nujol) along
with an intense ν(CO) absorption at 1887 cmϪ1. The stereo-
chemistry at ruthenium follows from the appearance of distinct
NCH3 environments [δ(1H) 2.31, 2.58], a singlet 31P-{1H} NMR
resonance (δ 8.2), and the virtual triplet patterns observed for
the phenyl resonances in the 13C NMR spectrum, characteristic
of a trans-Os(PPh3)2 arrangement.
solution and formation of the species [Os(CH᎐CHC H Me-
᎐
6
4
4)Cl(CO)(CNBut)(PPh3)2] 7a. The same isomer of 7a is
obtained on treating 6 with CNCMe3. Two intense absorptions
are noted in the infrared spectrum (CH2Cl2) at 2144 and 1943
cmϪ1 attributed to ν(CN) and ν(CO), respectively. A singlet
resonance observed at δ 0.97 in the 1H NMR spectrum is
assigned to the tert-butyl group in addition to a singlet at δ 2.25
for the tolyl methyl protons. The complex gives rise to an (AB)2
system at δ 6.80, 6.92 [J(AB) = 7.9 Hz] and a lower field reson-
ance at δ 7.89 due to the α-vinylic proton. This appears as a
doublet of triplets showing coupling to the two mutually trans
phosphines of 2.0 Hz as well as to the β-vinylic proton [J(Hα-
Hβ) = 18.3 Hz]. A fragmentation for loss of CNBut is observed
Although we have previously reported the synthesis of
ruthenatetraboranes of the form [RuR(B3H8)(CO)(PPh3)2] (R =
H, halide, aryl, vinyl or enynyl),9 the only known osmatetra-
borane is [OsH(B3H8)(CO)(PPh3)2] obtained from the reaction
of complex 1b with Tl[B3H8].27 The complex [Os(CH᎐CHC H -
᎐
6
4
Me-4)(B3H8)(CO)(PPh3)2] 9 is however readily obtained on
J. Chem. Soc., Dalton Trans., 1998, 3501–3510 3503

View Article Online
treatment of 4a with (less toxic) [NBun ][B3H8] in dichloro-
4)([9]aneS3)][BPh4]2.32 A reaction between 4a and [9]aneS3 was
4
methane. The inequivalence of the phosphine environments is
indicated by the AB system observed in the 31P-{1H} NMR
spectrum δ at 7.1, 7.9 with a coupling typical of a trans-OsP2
arrangement [J(AB) = 300.2 Hz]. The inequivalence of the two
phosphine environments arises from the butterfly “OsB3”
arrangement which provides endo and exo sites for the two
phosphines. Broad resonances arising from the two distinct
Os(µ-H)B protons of the triborate ligand are observed at
found to proceed readily at room temperature to provide within
2 h the complex [Os(CH᎐CHC H Me-4)(CO)(PPh )([9]aneS )]ϩ
᎐
6
4
3
3
12aϩ, which may be isolated as the hexafluorophosphate salt
12aؒPF6 in 66% yield. It is noteworthy that despite these mild
conditions no intermediate complex was observed involving
reduced denticity of the [9]aneS3 macrocycle in contrast to the
isolation of 10b above. The 31P-{1H} NMR spectrum comprises
a single resonance at δ 6.0 confirming that the macrocycle is
co-ordinated in a tridentate manner; bidentate co-ordination
would impose distinct chemical environments on the two phos-
phines (see above). The thiacycle gives rise to multiplet reson-
ances between δ 1.73 and 3.06 in the 1H NMR spectrum, due to
the chirality at osmium rendering each of the twelve proton
environments chemically distinct. The continuing presence of
the vinyl ligand is confirmed by the resonances at δ 7.68 [dd, Hα,
J(HαHβ) = 17.1, J(HαP) = 5.1 Hz] and 6.64 (d, Hβ). Fragmen-
tation of the [9]aneS3 ligand is observed under FAB MS condi-
tions involving loss of units of ethene at m/z = 721 for [M Ϫ
2C2H4]ϩ in addition to a molecular ion apparent at m/z = 779.
In a similar manner the phenyl complex [Os(C6H5)(CO)-
(PPh3)([9]aneS3)]ϩ could be isolated as the PF6 salt 12bؒPF6
from the reaction of [Os(C6H5)Cl(CO)(PPh3)2] with [9]aneS3
and NH4PF6. Spectroscopic data (Experimental section) which
characterise 12bؒPF6 are directly comparable to those for
12aؒPF6 and call for no further comment.
1
δ Ϫ9.70 and Ϫ8.54 in the H NMR, along with broad reson-
ances to lower field for the terminal and B(µ-H)B protons and
typical features due to the vinyl ligand. The 11B NMR spectrum
comprises two resonances at δ 2.6 and Ϫ37.2. The 11B NMR
spectrum of [OsH(B3H8)(CO)(PPh3)2] comprises three reson-
ances at δ 1.0, Ϫ39.5 and Ϫ40.5.27 Thus, in the case of 9,
resonances for the two chemically inequivalent osmium bound
boron nuclei are not resolved. Given that the 31P-{1H} NMR
spectrum is a sharply defined AB system, it may be assumed
that this coincidence of resonances is due to an insensitivity of
chemical shift towards the trans influences of the carbonyl and
vinyl ligands rather than a fluxional process involving rotation
of the ligand, which would chemically equilibrate the two
phosphine environments.
The complexes [Ru(R)Cl(CO)(PPh3)2] (R = aryl, vinyl or
enynyl) react with K[HB(pz)3] (pz = pyrazol-1-yl) to provide
the chiral monophosphine derivatives [RuR(CO)(PPh3)-
{HB(pz)3}].8 More recently we have isolated the complexes
[RuH(CA)(PPh3)2{η2-HB(pz)3}] (A = O or S) as inter-
mediates in the formation of [RuH(CA)(PPh3){HB(pz)3}] from
[RuH(Cl)(CA)(PPh3)3] and K[HB(pz)3],28 building on similar
observations by Esteruelas for related reactions of [MH(Cl)-
(CO)(PPri3)2] (M = Ru or Os).29 In the reactions of the σ-
organyl complexes of ruthenium no such intermediate was
observed, however the complex [Os(C6H5)(CO)(PPh3)2{η2-
HB(pz)3}] 10a could be isolated from the reaction of
[Os(C6H5)Cl(CO)(PPh3)2] and K[HB(pz)3], and subsequently
converted thermally (toluene reflux) into [Os(C6H5)(CO)-
(PPh3){HB(pz)3}] 11a.28 By analogy, the reaction of K[HB(pz)3]
with 4a in dichloromethane at room temperature provides the
Alkynyl complexes (Scheme 3)
We have previously shown that the reactions of Group 8
hydrido complexes, LnMH, with bis(alkynyl)mercurials [Hg-
᎐
(C᎐CR) ] can (to date) take one of three interrelated courses:
᎐
2
5,19
᎐
(i) formation of enynyl derivatives L(nϪ1)MC(C᎐CR)᎐CHR;
(ii) formation of alkynyl complexes L MC᎐CR or (iii) cata-
᎐
᎐
20
᎐
᎐
n
lytic formation of 1,3-diynes and reformation of the original
hydride complex.20 Amongst the hydride complexes which fall
into the second category is the BSD complex 2b and the result-
᎐
ing product [Ru(C᎐CR)Cl(CO)(BSD)(PPh ) ] serves as a pre-
᎐
3
2
cursor to other alkynyl complexes due to the lability of the BSD
ligand. The reaction of 2c with bis(4-ethynyltolyl)mercury()
was therefore investigated, given that it has already been noted
complex
[Os(CH᎐CHC H Me-4)(CO)(PPh ) {η2-HB(pz) }]
᎐
6 4 3 2 3
10b. This formulation was assigned principally on the basis of
the AB system observed in the 31P-{1H} NMR spectrum at
δ Ϫ1.8 and 0.8 [J(AB) = 348.8 Hz] which clearly indicated non-
equivalence of phosphine environments. This may be compared
with the values reported for 10a [δ 2.34, Ϫ2.62, 2J(AB) = 301.8
Hz].28 In the 1H NMR spectrum seven resonances are observed
in characteristic chemical shift positions for the pyrazolyl pro-
tons showing typical 3J(HH) couplings of approximately 2 Hz.
The remaining two resonances are presumed to be obscured
by phosphine activity. The FAB mass spectrum exhibited no
molecular ion, but instead a fragmentation for [M Ϫ CO]ϩ at
m/z = 1048. Tridentate co-ordination of the ‘scorpionate’
pyrazolylborate ligand is achieved by heating 10b under reflux
in toluene. The ν(CO) absorption (CH2Cl2) at 1913 cmϪ1 in the
precursor is shifted marginally to 1918 cmϪ1 for the resulting
above that 1b fails to provide an alkynyl complex, but is rather
᎐
recovered after catalysing the formation of (C᎐CC H Me-4) .
᎐
6
4
2
Stirring a dichloromethane solution of 2c with a slight excess (2
᎐
equivalents) of [Hg(C᎐CC H Me-4) ] resulted in a change to
᎐
6
4
2
deep red and deposition of elemental mercury. The brick-red
product, which could be isolated by addition of ethanol, was
᎐
found to be [Os(C᎐CC H Me-4)Cl(BTD)(CO)(PPh ) ] 13, by
᎐
6
4
3 2
analogy with the related ruthenium chemistry and in contrast
to the behaviour of 1b. This complex also results in good yield
from the reaction of 2c or 4a with an excess of 4-ethynyl-
toluene in refluxing tetrahydrofuran. Two characteristic absorp-
tions in the infrared spectrum (Nujol) at 2105 and 1920 cmϪ1
᎐
may be assigned to ν(C᎐C) and ν(CO) vibrations, respectively.
᎐
1
The H NMR spectrum included resonances at δ 2.29 (CH3)
monophosphine product [Os(CH᎐CHC H Me-4)(CO)(PPh )-
and 7.41 [C6H4; J(AB) = 8.2 Hz, second doublet obscured by
PPh3] due to the tolyl group. The FAB mass spectrum revealed
a molecular ion at m/z = 1031 (3%), however the heaviest pre-
dominant peak was, unsurprisingly, that due to loss of the
BTD ligand at m/z = 894 (57%). Once again the BTD ligand
is assumed to be trans to the strongly trans-effective alkynyl
ligand.
᎐
6
4
3
{HB(pz)3}] 11b. This species gives rise to a singlet resonance at
δ 11.2 in the 31P-{1H} NMR spectrum. The spectroscopic data
associated with the vinyl ligand and its substituents remain
essentially unchanged. Little change (ca. 0.2 ppm) is also
observed in the chemical shift values for the pyrazolyl protons
despite the transformation between bidentate and tridentate
co-ordination.
The similarity between the co-ordination chemistry of the
anionic ‘HB(pz)3’ ligand and the neutral macrocycle 1,4,7-
trithiacyclononane [9]aneS3 follows from both showing a strong
tendency to adopt a facial 6-electron donor co-ordination
mode.10,30,31 The organometallic chemistry of this ligand to
osmium is however limited to the hydride complex [OsH(CO)-
(PPh3)([9]aneS3)]PF6 and the arene complex [Os(η-MeC6H4Pri-
Treatment of complex 13 with Na[S2CNMe2]ؒ2H2O provides
᎐
the brown species [Os(C᎐CC H Me-4)(S CNMe )(CO)(PPh ) ]
᎐
6
4
2
2
3 2
᎐
14 which displays ν(C᎐C) and ν(CO) absorptions in the infrared
᎐
spectrum (Nujol) at 2088 and 1916 cmϪ1, respectively, to
slightly lower energy of those for the precursor 13. The data
for this complex are similar to those of the precursor with the
exception of the features that arise from the dithiocarbamate
ligand: as with 8, two singlet resonances are observed in the 1H
3504
J. Chem. Soc., Dalton Trans., 1998, 3501–3510

View Article Online
NMR spectrum at δ 2.24 and 2.30 corresponding to the chem-
ically distinct methyl groups of the dithiocarbamate ligand,
supporting the proposed stereochemistry. Two alternative
routes to the complex 14 were also developed: the reaction
between 3aؒClO4 and Na[S2CNMe2] provides high yields of the
S
C
Os
Ph
C
L
C
L
Ph
(i)38
complex [OsH(S2CNMe2)(CO)(PPh3)2], which on heating with
᎐
[Hg(C᎐CC H Me-4) ] in toluene produces 13. Alternatively, the
᎐
6
4
2
L
Os
L
᎐
Ph
Ph
H
reaction of 8 with an excess of HC᎐CC H Me-4 in refluxing
L
Os
L
᎐
6
4
Cl
S
(ii)
Cl
C
C
toluene provides good yields of 14. Recently, there have
appeared a number of such alkenyl/alkynyl exchange reactions
based on ruthenium and osmium,16,33,34 although none involved
dithiocarbamate complexes. The presumed mechanism of
ultimate σ metathesis most likely involves oxidative addition
of the terminal alkyne to provide a metal() species which sub-
sequently reductively eliminates alkene. The growing ubiquity
of formally tetravalent intermediates or isolated compounds in
the organometallic chemistry of ruthenium and osmium is an
emergent feature of the last decade. In part this may be due
to the increasing popularity of highly basic (and sterically
demanding) trialkylphosphines. Such tetravalent species are
also apparently mechanistically significant for PPh3 complexes
of these metals. They are however seldom observed, presum-
ably because the less basic triarylphosphine is less effective in
prolonging the lifetime of these more electronegative oxid-
ation states. For the alkenyl/alkynyl σ-metathesis process to be
facile, a vacant co-ordination site is desirable for the oxidative
addition step to proceed. The strong chelation of the dithio-
carbamate ligand is presumably responsible for the compar-
atively high temperatures required in the present process
(110 ЊC), which probably proceeds via phosphine dissociation
rather than chelate opening. As with the vinyl complex 8,
treatment of 13 with CNCMe3 provides the orange-brown
H
OC
C
CS
C
C
Ph
Ph
L
Os
L
L
Os
L
MeCN
MeCN
S
C
Cl
H
CS
OC
H
R
C
C
3b+
17
H
(iii)
(ii)
R
H
L
Os
L
H
L
Os
L
Cl
BTD
Cl
C
C
H
CS
(iv)
BTD
CS
16
2d
Scheme 4 L = PPh3, R = C6H4Me-4. Reagents: (i) HCl; (ii) CO;38
(iii) [Et4N]Cl, BTD; (iv) HC᎐CR.
᎐
᎐
absorption which appears at 1272 cmϪ1 in the infrared spec-
trum. The one previous example of an osmium vinylthio-
carbonyl complex [Os(CPh᎐CHPh)Cl(CS)(PPh ) ] results from
᎐
3
2
᎐
the reaction of the tolane complex [Os(PhC᎐CPh)(CS)(PPh ) ]
᎐
3
2
with hydrogen chloride.38 This complex is so far unique because
᎐
t
the synthetic route to [Os(PhC᎐CPh)(CS)(PPh ) ] from
[Os(CO)(CS)(PPh ) ] and PhC᎐CPh is not yet generally applic-
᎐
᎐
3
2
isocyanide adduct [Os(C᎐CC H Me-4)Cl(CO)(CNBu )(PPh ) ]
᎐
6
4
3 2
᎐
᎐
3
3
15 which displays two intense absorptions at 2157 and 1961
cmϪ1 in the infrared spectrum (CH2Cl2) for the ν(CN) and
able to other alkynes, e.g. reaction of [Os(CO)(CS)(PPh3)3] with
ethyne provides instead the osmaarene [Os(SCCHCHCHCH)-
ν(CO) absorptions, respectively. The comparatively weak
(CO)(PPh3)2].39 The complex [Os(CPh᎐CHPh)Cl(CS)(PPh ) ]
᎐
᎐
3
2
ν(C᎐C) is not however unambiguously identifiable. The
᎐
reacts with carbon monoxide to provide the thiostilbenoyl
methyl substituents of the isocyanide ligand give rise to a
complex [Os(η2-SCCPh᎐CHPh)Cl(CO)(PPh ) ] in an analo-
1
᎐
3
2
singlet resonance (δ 0.84) in the H NMR spectrum to higher
gous manner to the carbonylation of [Os(C6H4Me-4)Cl(CS)-
field than the methyl resonance of the acetylide ligand at
δ 2.23.
(PPh3)2].40 The vinyl complex [Os(CH᎐CHC H Me-4)Cl(CS)-
᎐
6
4
(BTD)(PPh3)2] 16 may be assumed to be in equilibrium with the
co-ordinatively unsaturated complex [Os(CH᎐CHC H Me-4)-
Cl(CS)(PPh3)2] and accordingly this was treated with a stream
᎐
6
4
Thiocarbonyl complexes (Scheme 4)
of carbon monoxide. The resulting product proved to be the
In our studies of carbonyl vinyl complexes of ruthenium we
have found it useful also to study, in parallel, the chemistry of
the thiocarbonyl analogues, where possible. This is due to the
clearly enhanced propensity of thiocarbonyl ligands to enter
into migratory insertion processes.10,35–41 Two recent observ-
thiocinnamoyl complex [Os(η2-SCCH᎐CHC H Me-4)Cl(CO)-
᎐
6
4
(PPh3)2] 17, in contrast to the formation of 7b upon carbonyl-
ation of 4b. No intermediate was isolated from this reaction.
The infrared spectrum of 17 (Nujol), whilst devoid of the char-
acteristic absorption for a terminal thiocarbonyl ligand, con-
tained a series of bands at 1589, 1562, 1326, 1307, 1287, 1241,
970 and 919 cmϪ1 which are typical of such a metallathiirene
motif.10,38–41,43,44
ations serve to highlight this process. (i) Whilst [Ru(CH᎐
᎐
CHC6H4Me-4)Cl(CO)(PPh3)2] reacts with [9]aneS3 and [NH4]-
PF6 to provide the vinyl salt [Ru(CH᎐CHC H Me-4)(CO)-
᎐
6
4
(PPh3)([9]aneS3)]PF6, the thiocarbonyl analogue provides a thio-
cinnamoyl complex [Ru(η2-SCCH᎐CHC H Me-4)(PPh )([9]-
᎐
6
4
3
aneS3)]PF6;10 (ii) Roper and co-workers37 have shown that the
ruthenium silyl complexes [Ru(SiR3)Cl(CA)(PPh3)2] (A = O or
S) react rapidly with CO to provide, respectively, [Ru(SiR3)Cl-
(CO)2(PPh3)2] and the novel silathioacyl complex [Ru(η2-
SCSiR3)Cl(CO)(PPh3)2], thereby showing that these ideas are
not limited to carbon-based migrating ligands.
Conclusion
The results described above taken together illustrate that there
is indeed a potentially rich alkyne-derived organometallic chem-
istry for the “OsH(Cl)(CO)(PPh3)2” fragment. The obstacle to
such chemistry appears to be the unsuitability of complex 1b as
a reagent due to the lesser tendency of PPh3 to dissociate under
mild conditions. This problem has been overcome by conver-
sion into the more labile complex [OsH(Cl)(CO)(BTD)(PPh3)2]
2c, which appears to provide synthetically useful amounts of
the desired 16-electron species “OsH(Cl)(CO)(PPh3)2” in solu-
tion. This breakthrough has provided access to new alkenyl,
alkenynyl, alkynyl and thioacyl complexes of divalent osmium,
which in contrast to the rapidly developing chemistry of [OsH-
(Cl)(CO)(PPri3)2] involves air-stable compounds throughout.
Furthermore, entry points into the organometallic chemistry of
The possibility of applying the principles above to osmium
thiocarbonyl chemistry was also therefore briefly investigated:
the complex [OsH(Cl)(CS)(PPh3)3] 1c42 was treated in a com-
pletely analogous manner to 1b to provide the salt [OsH(CS)-
(NCMe)2(PPh3)2]ClO4 3bؒClO4 which reacts with [NEt4]Cl
and BTD to provide [OsH(Cl)(CS)(BTD)(PPh3)2] 2d in 99%
yield. This species reacted immediately with 4-ethynyltoluene
to provide [Os(CH᎐CHC H Me-4)Cl(CS)(BTD)(PPh ) ] 16.
᎐
6
4
3 2
Spectroscopic data for 16 are immediately comparable to those
for 4a with the exception of the characteristically intense ν(CS)
J. Chem. Soc., Dalton Trans., 1998, 3501–3510
3505

View Article Online
osmium complexes of [9]aneS3, HB(pz)3 and triborate ligands
have been demonstrated. The utility of [OsH(CO)(NCMe)2-
(PPh3)2]ClO4 3aؒClO4 and [OsH(Cl)(CS)(BTD)(PPh3)2] 2d as
alternative synthons for alkyne hydroosmation has also been
briefly shown to offer promise.
0.35 g (99%). IR: (CH2Cl2) 2121 [ν(OsH)] cmϪ1; (Nujol) 2134
[ν(OsH)], 1290 [ν(CS)], 1267, 1184, 925, 890, 865 and 838 cmϪ1
.
1
NMR (CDCl3, 25 ЊC): H, δ Ϫ11.35 [t, 1 H, OsH, J(HP) =
16.2], 7.11–7.70 (m, 32 H, PC6H5 ϩ BTD) and 7.88 [d, 2 H,
BTD, J(HH) = 7.9 Hz]; 31P-{1H}, δ 21.1. FAB MS: m/z (%) 932
(3, [M]ϩ), 967 (4, [M Ϫ Cl]ϩ), 796 (52, [M Ϫ BTD]ϩ) and 759
(15, [M Ϫ Cl Ϫ BTD]ϩ) (Found: C, 55.4; H, 3.9; N, 2.9%. Calc.
for C43H35ClN2OsP2S2: C, 55.5; H, 3.8; N, 3.0%).
Experimental
General comments
[Os(CH᎐CHC H Me-4)Cl(CO)(BTD)(PPh ) ] 4a. The com-
᎐
6
4
3 2
All experiments were routinely carried out under aerobic condi-
tions unless otherwise stated. Solvents were used as received
from commercial sources. The complexes [OsH(Cl)(CO)-
(PPh3)3],2 [OsH(Cl)(CS)(PPh3)3]42 and [OsH(CO)(NCMe)2-
plex [OsH(Cl)(CO)(BTD)(PPh3)2] 2c (0.57 g, 0.62 mmol) was
dissolved in dichloromethane (20 cm3) and 4-ethynyltoluene
(0.16 cm3, 0.15 g, 1.26 mmol) added resulting in a purple solu-
tion. This was stirred for 10 min and then diluted with ethanol
(25 cm3). Purple crystals formed on slow reduction in solvent
volume (rotary evaporation) which were filtered off, washed
with ethanol (20 cm3), light petroleum (20 cm3) and dried in
vacuo. Yield: 0.62 g (97%). IR: (CH2Cl2) 1913 [ν(CO)], 1606
cmϪ1; (Nujol) 1899 [ν(CO)], 1604, 1571, 1546, 1311, 1270, 923,
23
(PPh3)2]ClO4 and the reagents [NBu4][B3H8],45 K[HB(pz)3]46
20,25
᎐
and (C᎐CC H Me-4)
have been described elsewhere. The
᎐
6
4
2
complex [Os(C6H5)Cl(CO)(PPh3)2] was prepared according to
the method described for the synthesis of [Os(C6H4Me-4)-
Cl(CO)(PPh3)2].40 Infrared, NMR and FAB MS data were
obtained using a Mattson Research Series IR spectrometer,
JEOL JNM-EX270, and Autospec Q instruments, respect-
ively. Phosphine-associated infrared data are not reported.
1
906, 875, 838 and 825 cmϪ1. NMR (CDCl3, 25 ЊC): H, δ 3.03
(s, 3 H, CH ), 5.87 [d, 1 H, ᎐CH, J(H H ) = 16.5], 6.84, 6.97
᎐
3
α
β
[(AB)2, 4 H, C6H4, J(AB) = 7.9], 7.03–7.44 (m, 34 H, C6H5 ϩ
1
Typically, H NMR resonances for the BTD and BSD ligands
BTD) and 9.08 [dt, 1 H, OsCHα, J(HαHβ) = 17.2, J(HαP) = 2.6
were obscured by phosphine resonances; “tv” indicates a vir-
tual triplet with ‘apparent’ coupling constants given. The 13C
NMR resonances were indicative of a trans bis(phosphine)
arrangement. The FAB mass spectra were obtained from
3-nitrobenzyl matrices; assignments are denoted by the most
intense peak of isotopic envelopes confirmed by simulation
and for salts Mϩ refers to the cationic complex. Micro-
analytical data were obtained from the Imperial College
and University of North London Microanalytical services.
Hz]; 13C-{1H} (CDCl3–CH2Cl2 1:10),
δ 182.2 [t, CO,
J(PC) = 8.6], 154.0 (m, Cα), 139.7, 137.9 (d × 2, BTD), 134.0 [tv,
C2,6 (C6H5), J(PC) = 4.9], 133.1 [C4 (C6H4)], 132.5 [t, Cβ,
J(PC) = 10.2], 131.3 [tv, C1 (C6H5), J(PC) = 24.3], 129.5 [C1
(C6H5)], 128.8 [s(br), C1 (C6H4)], 128.5 [s, C2,6 (C6H4)], 127.3 [tv,
C3,5 (C6H5), J(PC) = 4.3 Hz], 124.1 [C3,5 (C6H4)], 122.4, 120.5
(BTD) and 20.7 (CH3); 31P-{1H}, δ Ϫ1.0. FAB MS: m/z (%) =
896 (73, [M Ϫ BTD]ϩ), 779 (22, [M Ϫ vinyl Ϫ BTD]ϩ), 753
(5, [M Ϫ CO Ϫ vinyl]ϩ), 743 (22, [M Ϫ Cl Ϫ vinyl]ϩ), 634 (9,
[M Ϫ PPh3]ϩ) and 606 (23, [M Ϫ CO Ϫ PPh3]ϩ) (Found: C,
55.8; H, 3.7; N, 2.4. Calc. for C52H43ClN2OsOP2Sؒ1.5CH2Cl2:
C, 55.4; H, 4.0; N, 2.4%).
1
Crystal solvates were confirmed by H NMR integration for
dichloromethane, however this was not always possible for
chloroform solvates due to overlap with phosphine resonances,
or adventitious CHCl3 present in the deuteriated NMR solvent.
Light petroleum refers to that fraction of boiling range 40–
60 ЊC. The majority of complexes reported could be recrystal-
lised from mixtures of dichloromethane or chloroform and
ethanol.
[Os(CH᎐CH )Cl(CO)(BTD)(PPh ) ] 4b. Complex 2c (0.18 g,
᎐
2
3 2
0.17 mmol) was dissolved in dichloromethane (20 cm3) and
a stream of ethyne passed through the suspension for 30 s
resulting in a red solution. The flask was stoppered and the
mixture stirred for 40 min under an atmosphere of ethyne.
Ethanol (25 cm3) was then added and the total solvent vol-
ume slowly reduced to provide red crystals. These were fil-
tered off, washed with ethanol (20 cm
Preparations
[OsH(Cl)(CO)(BTD)(PPh3)2] 2c. The complex [OsH(CO)-
(NCMe)2(PPh3)2]ClO4 (1.00 g, 1.08 mmol) was dissolved in
dichloromethane (100 cm3) to give a colourless solution. To this
was added a solution of 2,1,3-benzothiadiazole (BTD: 0.44 g,
3.24 mmol) and [NEt4]Cl (0.54 g, 3.26 mmol) in ethanol (20
cm3). The mixture was heated for 1 h under reflux and then
diluted with ethanol (50 cm3). On slow concentration under
reduced pressure orange crystals formed, which were filtered
off, washed with ethanol (30 cm3) and light petroleum (30 cm3)
and dried in vacuo. Yield: 0.96 g (97%). IR: (CH2Cl2) 1982
[ν(OsH)], 1914 cmϪ1 [ν(CO)]. (Nujol) 2146, 2129, 1974 [ν(OsH)],
1905 [ν(CO)], 1720, 1529, 1311, 1276, 925, 871, 848 and 831
cmϪ1. NMR (CDCl3, 25 ЊC): 1H, δ Ϫ15.00 [t, 1 H, OsH,
J(HP) = 16.2], 7.09–7.66 (m, 32 H, C6H5 ϩ BTD) and 7.82 [d,
2 H, BTD, J(HH) = 9.3 Hz]; 31P-{1H}, δ 20.7. FAB MS: m/z
(%) = 780 (4, [M Ϫ BTD]ϩ), 741 (9, [M Ϫ Cl]ϩ) and 713 (3,
[M Ϫ Cl Ϫ CO]ϩ) (Found: C, 56.3; H, 3.8; N, 2.9. Calc. for
C43H35ClN2OOsP2S: C, 56.4; H, 3.9; N, 3.1%).
3) and light petroleum
(20 cm3) and dried in vacuo. Yield: 0.14 g (87%). IR:
(CH2Cl2) 1907 cmϪ1 [ν(CO)]; (Nujol) 1907 [ν(CO)], 1658,
1587, 1556, 1531, 1334, 1313, 1272, 1263, 925, 881, 846 and
823 cm
Ϫ1. NMR (CDCl3, 25 ЊC): 1H, δ 4.88 [d, 1 H, Hβ,
J(HαHβ) = 17.6], 5.96 [dd, 1 H, HβЈ, J(HαHβЈ) = 10.6, J(HβHβЈ) =
2.2 Hz], 7.30, 7.04, 8.05 (m × 3, 34 H, C6H5 ϩ BTD) and 8.57
(m, 1 H, Hα); 31P-{1H}, δ Ϫ1.3. FAB MS: m/z (%) = 936 (4,
[M]ϩ), 913 (7, [M Ϫ CO]ϩ), 905 (4, [M Ϫ Cl]ϩ), 805 (2,
[M Ϫ BTD]ϩ), 779 (5, [M Ϫ vinyl Ϫ BTD]ϩ), 743 (4, [M Ϫ
Cl Ϫ CO Ϫ BTD]ϩ) and 713 {4, [Os(PPh3)2]ϩ} (Found: C, 55.7;
H, 4.1; N, 2.8. Calc. for C45H37ClN2OOsP2Sؒ0.5CH2Cl2: C, 55.5;
H, 3.9; N, 2.9%).
᎐
[Os{C(C᎐
CC
H Me-4)᎐CHC H Me-4}Cl(CO)(BTD)-
᎐
4 6 4
᎐
6
(PPh3)2] 4c. Complex 2c (0.27 g, 0.30 mmol) was suspended in
tetrahydrofuran (20 cm3) and 1,4-di(p-tolyl)butadiyne (0.14 g,
0.61 mmol) added. The reaction was heated under reflux for 1 h
under which ethanol (20 cm3) was added. The total solvent
volume was reduced to ca. 15 cm3 under reduced pressure to
provide purple crystals. These were filtered off, washed with
[OsH(Cl)(CS)(BTD)(PPh3)2] 2d. The complex [OsH(CS)-
(NCMe)2(PPh3)2]ClO4 (3bؒClO4: 0.40 g, 0.43 mmol) was dis-
solved in dichloromethane (50 cm3) to give a colourless solu-
tion. 2,1,3-Benzothiadiazole (0.17 g, 1.25 mmol) and [NEt4]Cl
(0.21 g, 1.27 mmol) were added as an ethanolic solution (20
cm3). The mixture was heated for 1 h under reflux. Further
ethanol (30 cm3) was added and yellow crystals formed on
rotary evaporation. These were filtered off, washed with ethanol
(30 cm3) and light petroleum (30 cm3) and dried in vacuo. Yield:
ethanol (20 cm3) and light petroleum (20 cm3) and dried in
᎐
vacuo. Yield: 0.30 g (87%). IR: (CH Cl ) 2164, 2142 [ν(C᎐C)],
᎐
2
2
1909 cmϪ1 [ν(CO)]; (Nujol) 2158, 2136 [ν(C᎐C)], 1897 [ν(CO)],
᎐
᎐
1719, 1603, 1587, 1571, 1528, 1504, 1308, 1270, 1175, 924, 892,
1
875, 846 and 811 cmϪ1. NMR (CDCl3, 25 ЊC): H, δ 2.25, 2.38
(s × 2, 3 H × 2, CH3), 6.90 [(AB)2, only one doublet visible, 2 H,
3506
J. Chem. Soc., Dalton Trans., 1998, 3501–3510

View Article Online
CC6H4, J(AB) = 7.9 Hz], 6.43 [s(br), 1 H, Hβ], 6.96–7.88 (m, 40
H, PC6H5, C6H4 ϩ BTD); 31P-{1H}, δ Ϫ0.36. FAB MS: m/z
(%) = 1010 (13, [M Ϫ BTD]ϩ), 975 (13, [M Ϫ Cl Ϫ BTD]ϩ), 779
(5, M Ϫ BTD Ϫ vinyl]ϩ), 743 (14, [M Ϫ Cl Ϫ BTD Ϫ vinyl]ϩ)
and 713 {10, [Ru(PPh3)2]ϩ} (Found: C, 63.8; H, 4.3; N, 2.3.
Calc. for C61H49ClN2OOsP2S: C, 64.0; H, 4.3; N, 2.4%).
0.01 g, 0.09 mmol) added. After stirring for 10 min the solvent
volume was reduced to give a cream precipitate. This was fil-
tered off, washed with ethanol (20 cm3) and light petroleum (20
cm3) and dried. Yield: 0.03 g (64%). IR: (CH2Cl2) 2144 [ν(CN)],
1943 cmϪ1 [ν(CO)]; (Nujol) 2142 [ν(CN)], 1943 [ν(CO)], 1889,
1571, 1542, 1307, 971, 937, 890 and 840 cmϪ1. NMR (CDCl3,
1
25 ЊC): H, δ 0.97 (s, 9 H, NCCH3), 2.25 (s, 3 H, CCH3), 5.88
[Os(CH᎐CHC H Me-4)(CO)(NCMe) (PPh ) ]ClO 5ؒClO4.
[d, 1 H, ᎐CH, J(HH) = 18.05], 6.80, 6.92 [(AB) , 4 H, C H ,
᎐
2 6 4
᎐
6
4
2
3
2
4
The complex [OsH(CO)(NCMe)2(PPh3)2]ClO4 3aؒClO4 (0.10 g,
0.11 mmol) was dissolved in dichloromethane (10 cm3) and 4-
ethynyltoluene (0.03 cm3, 0.03 g, 0.26 mmol) added. The mix-
ture was stirred for 3 h and then diluted with ethanol (20 cm3).
Brown crystals precipitated on rotary evaporation. These were
filtered off, washed with cold ethanol (2 cm3) and light petrol-
eum (20 cm3) and dried. Yield: 0.09 g (79%). NB: The product is
slightly soluble in ethanol. IR: (CH2Cl2) 1945 cmϪ1 [ν(CO)];
(Nujol) 2328 [ν(NC)], 2292 [ν(NC)], 1940 [ν(CO)], 1722, 1573,
1548, 1506, 1313, 1091 (Td-ClO4Ϫ), 931, 846 and 817 cmϪ1
[δ(C6H4)]. NMR (CDCl3, 25 ЊC): 1H, δ 1.74, 1.85 (s × 2, 3
J(AB) = 7.92], 7.10–7.39 (m, 34 H, C6H5 ϩ BTD) and 7.89
[dt, 1 H, OsCH, J(HH) = 18.29, J(HP) = 1.97 Hz]; 31P-{1H},
δ Ϫ5.0. FAB MS (R = But): m/z (%) = 979 (13, [M]ϩ), 896 (15,
[M Ϫ CNR]ϩ), 862 (44, [M Ϫ vinyl]ϩ), 826 (7, [M Ϫ Cl Ϫ
vinyl]ϩ) and 779 (3, [M Ϫ vinyl Ϫ CNR]ϩ) (Found: C, 60.6; H,
4.8; N, 1.4. Calc. for C51H48ClNOsOP2Sؒ0.5CH2Cl2: C, 60.6;
H, 4.8; N, 1.4%).
[Os(CH᎐CHC H Me-4)Cl(CO) (PPh ) ] 7b. Complex 4a
᎐
6
4
2
3 2
(0.08 g, 0.08 mmol) was dissolved in dichloromethane (10 cm3)
and a stream of carbon monoxide passed through the suspen-
sion for 30 s immediately to give a pale yellow solution. The
flask was stoppered and stirred for 10 min under an atmosphere
of carbon monoxide. Ethanol (25 cm3) was added and on rotary
evaporation pink crystals formed which were filtered off,
washed with ethanol (20 cm3), hexane (20 cm3) and dried in
vacuo. Yield: 0.06 g (84%). IR: (CH2Cl2) 2021, 1953 cmϪ1
[ν(CO)]; (Nujol) 2011, 1947 (1935sh) [ν(CO)], 1716, 1313, 1278,
H × 2, NCCH ), 2.26 (s, 3 H, CH ), 5.53 [d, 1 H, ᎐CH ,
᎐
3
3
β
J(HαHβ) = 17.16], 6.69, 6.96 [(AB)2, 4 H, C6H4, J(AB) = 7.92],
7.41–7.57 (m, 30 H, C6H5) and 7.87 [dt, 1 H, OsCHα,
J(HαHβ) = 17.80, J(HP) = 2.64 Hz]; 31P-{1H}, δ 6.2. FAB MS:
m/z (%) = 945 (15, [M]ϩ), 902 (20, [M Ϫ MeCN]ϩ), 859 (42,
[M Ϫ 2MeCN]ϩ), 831 (32, [M Ϫ 2MeCN Ϫ CO]ϩ), 779 (40,
[M Ϫ vinyl Ϫ MeCN]ϩ), 743 (100, [M Ϫ vinyl Ϫ 2MeCN]ϩ)
and 713 {53, [Os(PPh3)2]ϩ}.
1
977 and 848 cmϪ1. NMR (CDCl3, 25 ЊC): H, δ 2.27 (s, 3 H,
CH ), 5.91 [dt, 1 H, ᎐CH , J(H H ) = 18.31, J(HP) = 2.24], 6.74,
᎐
3
β
α
β
[Os(CH᎐CHC H Me-4)Cl(CO)(NCMe)(PPh ) ] 6. (a) The
6.95 [(AB)2, 4 H, C6H4, J(AB) = 7.94], 7.33, 7.62 (m × 2, 30 H,
C6H5) and 7.47 [dt, 1 H, OsCHα J(HH) = 18.55, J(HP) = 6.18
Hz]; 31P-{1H}, δ 6.45. FAB MS: m/z (%) = 924 (4, [M]ϩ), 896
(100, [M Ϫ CO]ϩ), 807 (15, [M Ϫ vinyl]ϩ), 779 (18, [M Ϫ
vinyl Ϫ CO]ϩ), 771 (20, [M Ϫ Cl Ϫ vinyl]ϩ), 741 (10, [M Ϫ
Cl Ϫ CO Ϫ vinyl]ϩ), 606 (30, [M Ϫ 2CO Ϫ PPh3]ϩ), 451 (15,
[OsPPh3]ϩ) and 263 (48, [HPPh3]ϩ) (Found: C, 61.0; H, 4.4.
Calc. for C47H39ClO2OsP2: C, 61.1; H, 4.3%).
᎐
6
4
3 2
complex [Os(CH᎐CHC H Me-4)(CO)(NCMe) (PPh ) ]ClO
᎐
6
4
2
3
2
4
5ؒClO4 (0.10 g, 0.10 mmol) was dissolved in dichloromethane
(10 cm3) and [NEt4]Cl (0.04 g, 0.24 mmol) added as an eth-
anolic solution (10 cm3). The mixture was stirred and warmed
for 20 min to give a yellow solution. All solvent was removed
and the crude product extracted into dichloromethane (10 cm3)
and the extracts filtered. On evaporation of all solvent from
the filtrate and trituration in diethyl ether (25 cm3), colourless
crystals were obtained. These were filtered off, washed with
diethyl ether (10 cm3) and light petroleum (10 cm3) and dried in
vacuo. Yield: 0.06 g (58%).
[Os(CH᎐CHC H Me-4)(S CNMe )(CO)(PPh ) ] 8. Complex
᎐
6
4
2
2
3 2
4a (0.07 g, 0.07 mmol) was dissolved in dichloromethane (20
cm3) and a solution of Na[S2CNMe2] (0.02 g, 0.14 mmol) in
ethanol (5 cm3) added. The mixture was stirred for 30 min and
then diluted with ethanol (20 cm3). Yellow crystals precipitated
on rotary evaporation which were filtered off, washed with
ethanol (20 cm3) and light petroleum (20 cm3) and dried in
vacuo. Yield: 0.06 g (88%). IR: (CH2Cl2) 1893 cmϪ1 [ν(CO)];
(Nujol) 1887 [ν(CO)], 1718, 1585, 1569, 1521, 1504, 1307,
(b) A sample of the complex [Os(CH᎐CHC H Me-4)-
᎐
6
4
Cl(CO)(BTD)(PPh3)2] 4a was recrystallised from a mixture of
acetonitrile and hexane to which sufficient dichloromethane
had been added to ensure homogeneity. Yield quantitative. IR:
(CH2Cl2) 1920 cmϪ1 [ν(CO)]; (Nujol) 2022 [ν(NC)], 1909
[ν(CO)], 1720, 1604, 1671, 1544, 1311, 890, 846 and 790 cmϪ1
.
1
NMR (CDCl3, 25 ЊC): 1H, δ 1.57 (s, 3 H, NCCH3), 2.24 (s, 3 H,
CH ), 5.72 [d, 1 H, ᎐CH , J(H H ) = 17.16], 6.79, 6.92 [(AB) , 4
1255, 1153, 970, 848 and 831 cmϪ1. NMR (CDCl3, 25 ЊC): H,
δ 2.20 (s, 3 H, CH3), 2.31, 2.58 (s × 2, 3 H × 2, NCH3), 5.52
᎐
3
β
α
β
2
H, CC6H4, J(AB) = 8.26], 7.27, 7.66 (m × 2, 30 H, PC6H5) and
8.65 [dt, 1 H, OsCHα, J(HαHβ) = 17.16, J(HαP) = 2.31 Hz]; 31P-
{1H}, δ Ϫ1.1. FAB MS: m/z (%) = 896 (100, [M Ϫ MeCN]ϩ),
859 (14, [M Ϫ vinyl Ϫ MeCN]ϩ), 779 (22, [M Ϫ vinyl Ϫ
MeCN]ϩ), 743 (40, [M Ϫ vinyl Ϫ Cl Ϫ MeCN]ϩ), 713 {11,
[Os(PPh3)2]ϩ} and 606 (25, [M Ϫ MeCN Ϫ CO Ϫ PPh3]ϩ)
(Found: C, 63.5; H, 5.7; N, 1.1. Calc. for C51H48ClNOsOP2Sؒ
C6H12: C, 63.4; H, 5.7; N, 1.4%).
[d, 1 H, ᎐CH, J(HH) = 17.16], 6.40, 6.80 [(AB) , 4 H, C H ,
᎐
2 6 4
J(AB) = 7.92], 7.25–7.61 (m, 30 H, PC6H5), 8.36 [dt, 1 H,
OsCHα, J(HαHβ) = 17.16, J(HαP) = 2.65 Hz]; 13C-{1H} (CDCl3–
CH2Cl2 1:10), δ 208.0 (S2C), 186.1 [t, CO, J(PC) = 11.3], 140.8
[s(br), Cα], 134.8 [tv, C2,6 (C6H5), J(PC) = 4.9], 133.1 [tv, C1
(C6H5), J(PC) = 24.3], 132.8 [t, Cβ, J(PC) = 9.7], 132.3 [C4
(C6H4)], 132.0 [s(br), C1 (C6H4)], 129.2 [C4 (C6H5)], 128.2
[C3,5 (C6H4)], 127.2 [tv, C3,5 (C6H5), J(PC) = 4.9 Hz], 123.9
[C2,6 (C6H4)], 37.8, 37.0 (NCH3) and 20.6 (CH3); 31P-{1H},
δ 8.2. FAB MS: m/z (%) = 995 (2, [M ϩ H2O]ϩ), 982 (3, [M]ϩ),
878 (3, [M ϩ H2O Ϫ vinyl]ϩ) and 407 (56, [M Ϫ vinyl]ϩ)
(Found: C, 56.1; H, 4.3; N, 1.4. Calc. for C47H45NOOsP2S2ؒ
0.5CHCl3: C, 56.2; H, 4.5; N, 1.4%).
[Os(CH᎐CHC H Me-4)Cl(CO)(CNBut)(PPh ) ] 7a. (a) The
᎐
6
4
3 2
complex [Os(CH᎐CHC H Me-4)Cl(CO)(BTD)(PPh ) ] 4a
᎐
6
4
3 2
(0.08 g, 0.08 mmol) was dissolved in dichloromethane (10 cm3)
and tert-butyl isocyanide (0.01 cm3, 0.01 g, 0.09 mmol) added.
The reaction was stirred for 20 min to give a colourless solution.
Ethanol (20 cm3) was added and cream crystals precipitated on
rotary evaporation. These were filtered off, washed with ethanol
(20 cm3) and light petroleum (20 cm3) and dried. Yield: 0.06 g
(77%).
[Os(CH᎐CHC H Me-4)(B H )(CO)(PPh ) ] 9. Complex 4a
᎐
6
4
3
8
3 2
(0.30 g, 0.29 mmol) and [NBun ][B3H8] (0.09 g, 0.32 mmol) were
4
dissolved in a mixture of dichloromethane (20 cm3) and meth-
anol (10 cm3) and stirred for 4 h. All volatiles were removed
under reduced pressure. The crude product was extracted into
dichloromethane and passed through diatomaceous earth. The
solvent was removed from the filtrate and the residue crystal-
lised by ultrasonic trituration with diethyl ether (25 cm3) to
(b) Complex 5ؒClO4 (0.05 g, 0.05 mmol) was dissolved in
dichloromethane (10 cm3) and an ethanolic (15 cm3) solution of
[NEt4]Cl (0.02 g, 0.12 mmol) added. The mixture was stirred
and heated gently for 20 min and then CNCMe3 (0.01 cm3,
J. Chem. Soc., Dalton Trans., 1998, 3501–3510
3507

View Article Online
provide a red-brown microcrystalline solid. This was filtered
off, washed with diethyl ether (20 cm3), light petroleum (20 cm3)
and dried in vacuo. Yield: 0.15 g (57%). IR: (CH2Cl2) 2528, 2462
[ν(BH)], 1957 cmϪ1 [ν(CO)]; (Nujol) 2524, 2460, 2148 [ν(BH)],
2107, 2017 [ν(BHOs)], 1951 [ν(CO)], 1585, 1573, 1548, 1506,
1309, 921, 848 and 782 cmϪ1. NMR (CDCl3, 25 ЊC): 1H,
δ Ϫ9.70, Ϫ8.54 [s(br) × 2, 1 H × 2, µ(OsHB)], Ϫ0.57, Ϫ0.41,
1.60, 2.30, 3.32, 4.05 [s(vbr) × 6, 6 H, B–H and µ-B2H], 2.23
(s, 3 H, CH ), 6.09 [dt, 1 H, ᎐CH, J(HH) = 17.80, J(HP) un-
resolved], 6.36, 6.87 [(AB)2, 4 H, C6H4, J(AB) = 7.92 Hz] and
7.11–7.61 (m, 30 H, C6H5); 31P-{1H}, δ 7.1, 7.9 [AB, J(AB) =
300 Hz]; 11B, δ 2.6 (1 B) and Ϫ37.2 (2 B, OsB). FAB MS:
m/z (%) = 902 (25, [M]ϩ), 860 (6, [M Ϫ B3H8]ϩ), 744 (80,
[M Ϫ vinyl Ϫ B3H8]ϩ), 713 {11, [Ru(PPh3)2]ϩ} and 635 (13,
[M Ϫ PPh3]ϩ) (Found: C, 59.5; H, 4.8. Calc. for C46H47B3-
OOsP2ؒ0.5CH2Cl2: C, 59.2; H, 5.1%).
[Os(CH᎐CHC H Me-4)(CO)(PPh )([9]aneS )]PF 12aؒPF6.
᎐
6 4 3 3 6
Complex 4a (0.10 g, 0.10 mmol), 1,4,7-trithiacyclononane (0.03
g, 0.17 mmol) and [NH4]PF6 (0.03 g) were dissolved in a mix-
ture of dichloromethane (20 cm3) and ethanol (10 cm3). The
mixture was heated under reflux for 2 h and then all solvent
evaporated. The crude product was extracted into dichloro-
methane (2 × 10 cm3) and the combined extracts were filtered
through diatomaceous earth and then freed of volatiles under
reduced pressure. Diethyl ether (25 cm3) was added and an
ochre solid obtained by ultrasonic trituration. This was filtered
off, washed with diethyl ether (20 cm3), light petroleum (20 cm3)
and dried. Yield: 0.07 g (66%). IR: (CH2Cl2) 1964 cmϪ1 [ν(CO)];
(Nujol) 1955 [ν(CO)], 1716, 1606, 1575, 1548, 1160 and 833
cmϪ1 [ν(PF)]. NMR (CDCl3, 25 ЊC): 1H, δ 1.83, 2.14, 2.39, 2.64,
2.78, 3.00 (m × 6, 12 H, SCH2), 2.26 (s, 3 H, CH3), 6.64 [d, 1 H,
᎐
3
᎐CH , J(H H ) = 17.07], 6.79, 6.98 [(AB) , 4 H, C H , J(AB) =
᎐
β
α
β
2
6
4
8.04], 7.30–7.50 (m, 15 H, C6H5) and 7.68 [dd, 1 H, OsCHα,
J(HαHβ) = 17.07, J(HP) = 5.07 Hz]; 31P-{1H}, δ 6.0. FAB MS:
m/z (%) = 779 (100, [M]ϩ), 751 (4, [M Ϫ CO]ϩ), 721 (4, [M Ϫ
2C2H4]ϩ) and 634 (7, [M Ϫ CO Ϫ vinyl]ϩ). For microanalytical
purposes the tetraphenylborate salt 12aؒBPh4 was prepared by
employing NaBPh4 in place of [NH4]PF6 (Found: C, 63.8; H,
5.3. Calc. for C58H56BOOsPS3: C, 63.5; H, 5.1%).
[Os(CH᎐CHC H Me-4)(CO)(PPh ) {ç2-HB(pz) }]
10b.
᎐
6
4
3
2
3
Complex 4a (0.30 g, 0.29 mmol) and K[HB(pz)3] (0.11 g, 0.44
mmol) were dissolved in dichloromethane (20 cm3) and the mix-
ture stirred for 6 h. The purple solution was then filtered
through diatomaceous earth and the filtrate diluted with eth-
anol (20 cm3). A pale purple solid was obtained on reduction in
solvent volume. This was filtered off, washed with cold ethanol
(2 cm3), light petroleum (20 cm3) and dried in vacuo. Yield: 0.17
g (55%). IR: (CH2Cl2) 2466 [ν(BH)], 1918 cmϪ1 [ν(CO)] (Nujol)
2468 [ν(BH)], 1913 [ν(CO)], 1718, 1571, 1544, 1295, 1209, 1058,
1033, 985, 952, 919, 877 and 846 cmϪ1. NMR (CDCl3, 25 ЊC):
1H, δ 2.31 (s, 3 H, CH3), 5.67, 5.71 [t × 2, 1 H × 2, H4 (pz),
[Os(C6H5)(CO)(PPh3)([9]aneS3)]PF6 12bؒPF6. The complex
[Os(C6H5)Cl(CO)(PPh3)2] (0.25 g, 0.29 mmol) was dissolved in
a mixture of dichloromethane (20 cm3) and ethanol (10 cm3).
Ammonium hexafluorophosphate (0.10 g, 0.61 mmol) and
1,4,7-trithiacyclononane (0.10 g, 0.56 mmol) were added. The
mixture was heated under reflux for 10 min and then freed
of volatiles. The residue was extracted with dichloromethane
(2 × 10 cm3) and the combined extracts were filtered through
diatomaceous earth. The filtrate was diluted with toluene (20
cm3) and the solvent volume slowly reduced (rotary evaporator)
to provide colourless crystals. These were filtered off, washed
with toluene (20 cm3) and light petroleum (20 cm3) and dried in
vacuo. Yield: 0.17 g (67%). IR: (CH2Cl2) 1963 cmϪ1 [ν(CO)];
(Nujol) 1967 [ν(CO)], 1571, 1311, 1297, 968, 839, 904 and 838
cmϪ1 [ν(PF)]. NMR (CDCl3, 25 ЊC): 1H, δ 1.80, 2.17, 2.32, 2.45,
2.63–2.93, 3.10–3.18 (m × 6, 12 H, SCH2), 6.73–6.82 (m, 5 H,
RuC6H5) and 7.24–7.48 (m, 15 H, PC6H5); 31P-{1H}, δ 6.3. FAB
MS: m/z (%) 739 (100, [M]ϩ), 709 (2, [M Ϫ C2H4]ϩ), 683 (2,
[M Ϫ 2C2H4]ϩ), 449 (10, [M Ϫ CO Ϫ PPh3]ϩ), 419 (3, [M Ϫ
2C2H4 Ϫ PPh3]ϩ), 390 (3, [M Ϫ 3C2H4 Ϫ PPh3]ϩ) and 365 (5,
[M Ϫ CO Ϫ 3C2H4 Ϫ PPh3]ϩ) (Found: C, 42.8; H, 3.9. Calc. for
C31H32F6OOsP2S3: C, 42.2; H, 3.7%).
J(HH) = 2.2], 5.89 [d, 1 H, ᎐CH , J(H H ) = 17.07], 6.23 [t, 1 H,
᎐
β
α
β
H4 (pz), J(HH) = 2.0], 6.35 [d, 1 H, H3,5 (pz), J(HH) = 2.2], 6.77
[(AB)2, 4 H, CC6H4, J(AB) = 8.16, NB one doublet obscured],
6.92 [d, 1 H, H3,5 (pz), J(HH) = 2.2], 6.96–7.30 [m, 32 H,
C6H5 ϩ 2 H3,5 (pz)], 7.83 [d, 2 H, H3,5 (pz), J(HH) = 1.5] and
8.24 [dt, 1 H, OsCHα, J(HαHβ) = 17.32, J(HαP) = 2.49 Hz]; 31P-
{1H}, δ Ϫ1.8, 0.8 [AB, J(AB) = 348 Hz]. FAB MS: m/z
(%) = 1048 (36, [M Ϫ CO]ϩ), 955 (5, [M Ϫ vinyl]ϩ), 778 (18,
[M Ϫ PPh3]ϩ) and 693 (8, [M Ϫ vinyl Ϫ PPh3]ϩ) (Found: C,
61.7; H, 4.5; N, 7.7. Calc. for C55H49BN6OOsP2: C, 61.6; H, 4.6;
N, 7.8%).
[Os(CH᎐CHC H Me-4)(CO)(PPh ){HB(pz) }]
11b.
(a)
᎐
6
4
3
3
Complex 4a (0.08 g, 0.08 mmol) and K[HB(pz)3] (0.03 g, 0.12
mmol) were dissolved in toluene (20 cm3) and the mixture
heated under reflux for 5 min and then allowed to cool and
filtered through diatomaceous earth. All solvent was removed
from the filtrate under reduced pressure. Hexane (25 cm3) was
added to the residue and a cream solid obtained by ultrasonic
trituration. This was filtered off, washed with hexane (20 cm3)
and dried in vacuo. Yield: 0.05 g (77%).
[OsH(S2CNMe2)(CO)(PPh3)2]. Complex 3aؒClO4 (0.26 g,
0.28 mmol) was dissolved in dichloromethane (20 cm3) and a
solution of Na[S2CNMe2]ؒ2H2O (0.10 g, 0.70 mmol) in ethanol
(5 cm3) added. The mixture was heated under reflux for 10 min
and then diluted with ethanol (20 cm3). Colourless crystals pre-
cipitated on rotary evaporation which were filtered off, washed
with ethanol (20 cm3) and light petroleum (20 cm3) and dried in
vacuo. Yield: 0.20 g (8%). IR: (CH2Cl2) 2026 [ν(OsH)], 1903
cmϪ1 [ν(CO)]; (Nujol) 2043 [ν(OsH)], 1989, 1901 [ν(CO)], 1857,
(b) The complex [Os(CH᎐CHC H Me-4)(CO)(PPh ) {η2-
᎐
6
4
3 2
HB(pz)3}] 10b (0.05 g, 0.05 mmol) was dissolved in toluene (10
cm3) and the reaction heated under reflux for 2 min. The result-
ing solution was worked up as indicated in (a) above. Yield:
0.03 g (76%). The product can be recrystallised from benzene–
hexane mixtures. IR: (CH2Cl2) 2485 [ν(BH)], 1918 cmϪ1
[ν(CO)]; (Nujol) 2424, 2399 [ν(BH)], 1920 [ν(CO)], 1641, 1290,
1214, 1112, 1047, 966, 919, 883 and 848 cmϪ1. NMR (CDCl3,
25 ЊC): 1H, δ 2.31 (s, 3 H, CH3), 4.6 [s(br), 1 H, BH], 5.89, 5.93
[t × 2, 1 H × 2, H4 (pz), J(HH) = 2.2], 6.07 [t, 1 H, H4 (pz),
1584, 1571, 1514, 1310, 1260, 1156, 932, 898 and 852 cmϪ1
.
NMR (CDCl3, 25 ЊC): 1H, δ Ϫ12.93 [t, 1 H, OsH, J(HP) = 18.16
Hz], 2.37 (s, 6 H, NCH3), 7.27–7.34, 7.69–7.77 (m × 2, 30 H,
C6H5); 31P-{1H}, δ 18.8. FAB MS: m/z (%) = 880 (18, [M ϩ
H2O]ϩ), 865 (57, [M]ϩ), 832 (4, [M Ϫ CO]ϩ) and 603 (10, [M Ϫ
PPh3]ϩ) (Found: C, 55.1; H, 4.2; N, 1.7. Calc. for C40H37-
NOOsP2S2: C, 55.6; H, 4.3; N, 1.6%).
J(HH) = 2.2], 6.27 [d, 1 H, ᎐CH , J(H H ) = 17.07], 6.82 [appar-
᎐
β
α
β
ent “t” (2 × d), 2 H, H3,5 (pz), J(HH) = 1.9], 7.01–7.35 [m, 20 H,
PC6H5, C6H4 ϩH3,5 (pz)], 7.68 [apparent “t” (2 × d), 2 H, H3,5
(pz), J(HH) = 2.3], 7.78 [d, 1 H, H3,5 (pz), J(HH) = 2.0] and 8.54
[dd, 1 H, OsCHα, J(HαHβ) = 17.07, J(HαP) = 1.48 Hz]; 31P-{1H},
δ 11.2. FAB MS: m/z (%) = 812 (100, [M]ϩ), 743 (9, [M Ϫ pz]ϩ),
695 (14, [M Ϫ vinyl]ϩ), 666 (15, [M Ϫ vinyl Ϫ CO]ϩ), 627 (8,
[M Ϫ pz Ϫ vinyl]ϩ) and 597 {7, [M Ϫ HB(pz)3]ϩ} (Found: C,
59.4; H, 4.7; N, 9.4. Calc. for C37H34BN6OOsPؒ1.5C6H6: C,
59.6; H, 4.7; N, 9.1%).
᎐
[Os(C᎐CC H Me-4)Cl(CO)(BTD)(PPh ) ] 13. (a) Complex
᎐
6
4
3 2
2c (0.20 g, 0.22 mmol) was dissolved in tetrahydrofuran (20 cm3)
᎐
and [Hg(C᎐CC H Me-4) ] (0.18 g, 0.42 mmol) added. The
᎐
6
4
2
mixture was heated under reflux for 10 min and then all solvent
evaporated. Dichloromethane (20 cm3) was added, the solution
filtered through diatomaceous earth and the filtrate diluted with
3508
J. Chem. Soc., Dalton Trans., 1998, 3501–3510

View Article Online
ethanol (20 cm3). A brick-red solid was then obtained on rotary
evaporation. This was filtered off, washed with ethanol (5 cm3),
light petroleum (20 cm3) and dried in vacuo. Yield: 0.18 g (80%).
The product appears partially soluble in ethanol.
(b) Complex 2c (0.10 g, 0.11 mmol) or 4a (0.12 g, 0.11 mmol)
and 4-ethynyltoluene (0.30 g) were heated under reflux in tetra-
hydrofuran (15 cm3) for 1 h. The red solution was diluted with
ethanol (30 cm3) and concentrated under reduced pressure to
and CNCMe3 (0.1 cm3, excess) added. The mixture was stirred
for 3 h and all volatiles then removed. Hexane (20 cm3) was
added to the residue and an orange-brown solid obtained on
ultrasonic trituration. This was filtered off, washed with hexane
(20 cm3) and dried in vacuo. The crude product was recrystal-
lised from a mixture of dichloromethane and ethanol. Yield:
᎐
0.04 g (71%). IR: (CH Cl ) 2157 [ν(CN)], 2105 [ν(C᎐C)], 1961
᎐
2
2
cmϪ1 [ν(CO)]; (Nujol) 2148 [ν(CN)], 2102 [ν(C᎐C)], 1945
᎐
᎐
provide crystals of 13. Yield 0.080 g (71%). IR: (CH2Cl2) 2109
[ν(CO)], 1716, 1307, 1232, 1187, 1157, 971, 937, 890, 848 and
Ϫ1
1
815 cmϪ1 [δ(C6H4)]. NMR (CDCl3, 25 ЊC): H, δ 0.84 (s, 9 H,
᎐
᎐
[ν(C᎐C)], 1926 cm [ν(CO)]; (Nujol) 2105 [ν(C᎐C)], 1920
᎐
᎐
[ν(CO)], 1720, 1604, 1587, 1529, 1311, 1272, 1216, 925, 877 and
NCCH3), 2.23 (s, 3 H, CCH3), 6.67, 6.85 [(AB)2, 4 H, C6H4,
J(AB) = 7.8 Hz] and 7.08–7.97 (m, 30 H, PC6H5); 31P-{1H},
δ Ϫ7.1. FAB MS: m/z (%) (R = CMe3) = 1084 (20, [M ϩ
CNR ϩ CO]ϩ), 1057 (50, [M ϩ CNR]ϩ), 977 (62, [M]ϩ), 942
(29, [M Ϫ Cl]ϩ), 894 (11, [M Ϫ CNR]ϩ), 862 (84, [M Ϫ Cl Ϫ
acetylide]ϩ), 827 (22, [M Ϫ Cl Ϫ acetylide]ϩ) and 687 (20,
[M Ϫ CO Ϫ PPh3]ϩ) (Found: C, 62.7; H, 4.8; N, 1.4. Calc. for
C39H33ClP2RuS: C, 62.4; H, 4.6; N, 1.3%).
1
811 cmϪ1 [δ(C6H4)]. NMR (CDCl3, 25 ЊC): H, δ 2.29 (s, 3 H,
CH3), 7.41 [(AB)2, 2 H, C6H4, J(AB) = 8.19 Hz, NB second res-
onance obscured] and 7.03–7.85 (m, 36 H, PC6H5 ϩ C6H4 ϩ
BTD); 13C-{1H} (CDCl3–CH2Cl2 1:10), δ 179.8 [t, CO,
J(PC) = 8.6], 155.3, 153.8 (BTD), 134.1 [tv, C2,6 (C6H5),
J(PC) = 4.9], 131.6 [tv, C1 (C6H5), J(PC) = 24.8], 130.6 [C3,5
(C6H4)], 129.6 [C4 (C6H5)], 128.7 [C4 (C6H4)], 128.5 [C2,6 (C6H4)],
127.4 [tv, C3,5 (C6H5), J(PC) = 4.3], 126.3 [C1 (C6H4)], 122.7,
120.6 (BTD), 116.6 (s, Cβ), 84.5 [t, Cα, J(PC) = 14.0 Hz] and
21.0 (s, CH3); 31P-{ 1H}, δ 0.3. FAB MS: m/z (%) = 1031
(3, [M]ϩ), 894 (57, [M Ϫ BTD]ϩ), 857 (4, M Ϫ Cl Ϫ BTD]ϩ),
827 (6, [M Ϫ Cl Ϫ CO Ϫ BTD]ϩ), 779 (18, [M Ϫ acetylide Ϫ
BTD]ϩ) and 743 (14, [M Ϫ Cl Ϫ acetylide Ϫ BTD]ϩ) (Found:
C, 58.7; H, 4.0; N, 1.7. Calc. for C52H41ClN2OOsP2Sؒ0.5CH2-
Cl2: C, 58.8; H, 4.0; N, 2.6%).
[Os(CH᎐CHC H Me-4)Cl(CS)(BTD)(PPh ) ] 16. The com-
᎐
6
4
3 2
plex [OsH(Cl)(CS)(BTD)(PPh3)2] 2d (0.10 g, 0.11 mmol) was
dissolved in dichloromethane (20 cm3) and 4-ethynyltoluene
(0.02 cm3, 0.02 g, 0.16 mmol) added to give a purple solution.
This was stirred for 20 min and diluted with ethanol (25 cm3).
Pink crystals precipitated on rotary evaporation. These were
isolated, washed with ethanol (20 cm3), light petroleum (20 cm3)
and dried in vacuo. Yield: 0.08 g (71%). IR (Nujol): 1897, 1571,
1546, 1527, 1286, 1272 [ν(CS)], 1220, 923, 890, 875, 844, 825
᎐
[Os(C᎐CC H Me-4)(S CNMe )(CO)(PPh ) ] 14. (a) The
᎐
6
4
2
2
3 2
1
and 786 cmϪ1. NMR (CDCl3, 25 ЊC): H, δ 2.30 (s, 3 H, CH3),
complex [OsH(S2CNMe2)(CO)(PPh3)2] (0.10 g, 0.12 mmol) was
3
᎐
dissolved in toluene (20 cm ) and [Hg(C᎐CC H Me-4) ] (0.06 g,
᎐
6
4
2
5.98 [d(br), 1 H, ᎐CH , J(H H ) = 16.4], 6.91–7.47 (m, 38 H,
᎐
β
α
β
0.14 mmol) added. The mixture was heated under reflux for 8 h
and then freed of volatiles. The residue was extracted with
dichloromethane (20 cm3) and the extracts were filtered through
diatomaceous earth. Ethanol (20 cm3) was then added to the
filtrate and an ochre solid obtained on rotary evaporation. This
was filtered off, washed with ethanol (5 cm3), light petroleum
PC6H5, C6H4 ϩ BTD) and 9.01 [d(br), 1 H, OsCHα, J(HαHβ) =
18.1 Hz]; 31P-{1H}, δ Ϫ1.0. FAB MS: m/z (%) = 1047 (2, [M]ϩ),
1012 (9, [M Ϫ Cl]ϩ), 912 (70, [M Ϫ BTD]ϩ), 877 (12, [M Ϫ Cl Ϫ
BTD]ϩ), 795 (41, [M Ϫ vinyl]ϩ), 757 (20, [M Ϫ Cl Ϫ vinyl]ϩ),
650 (12, [M Ϫ BTD Ϫ PPh3]ϩ), 612 (12, [M Ϫ Cl Ϫ BTD Ϫ
PPh3]ϩ) and 495 {16, [Os(CS)(PPh3)]ϩ} (Found: C, 59.5; H, 4.1;
N, 2.7. Calc. for C52H43ClN2OsP2S2: C, 59.5; H, 4.1; N, 2.4%).
(20 cm3) and dried in vacuo. Yield: 0.09 g (77%).
᎐
(b) The complex [Os(C᎐CC H Me-4)Cl(CO)(BTD)(PPh ) ]
᎐
6
4
3 2
13 (0.10 g, 0.10 mmol) was dissolved in dichloromethane (10
cm3) and Na[S2CNMe2] (0.03 g, 0.21 mmol) added as an eth-
anolic solution (10 cm3). The reaction was stirred for 1 h and
then the solvent volume reduced. The resultant ochre precipi-
tate was filtered off, washed with ethanol (20 cm3), light petrol-
eum (20 cm3) and dried in vacuo. Yield: 0.08 g (82%).
[Os(ç2-SCCH᎐CHC H Me-4)Cl(CO)(PPh ) ] 17. The com-
᎐
6
4
3 2
plex [Os(CH᎐CHC H Me-4)Cl(CS)(BTD)(PPh ) ] 15 (0.10 g,
᎐
6
4
3 2
0.10 mmol) was dissolved in dichloromethane (10 cm3) and a
stream of carbon monoxide passed through the suspension for
30 s. On stirring for 20 min the red solution darkened. All
solvent was then removed and a dark red-brown product was
obtained by ultrasonic trituration in hexane (25 cm3). This was
filtered off, washed with hexane (10 cm3), and recrystallised
from a mixture of dichloromethane and ethanol. Yield: 0.07 g
(78%). IR: (CH2Cl2) 1899 cmϪ1 [ν(CO)]; (Nujol) 1895 [ν(CO)],
1714, 1589, 1562, 1326, 1307, 1287, 1241, 970, 919, 890 and
806 cmϪ1. NMR (CDCl3, 25 ЊC): 1H, δ 2.26 (s, 3 H, CH3), 6.24,
6.75 [(AB)2, 4 H, C6H4, J(AB) = 7.94], 7.00, 7.04 [AB, 2 H,
(c) Complex 4a (0.10 g, 0.10 mmol) was dissolved in toluene
(10 cm3) and 4-ethynyltoluene (0.1 cm3, excess) added. The
reaction was heated under reflux for 5 h and then all solvent
evaporated. An ochre precipitate was obtained by ultrasonic
trituration in ethanol (20 cm3). This was filtered off, washed
with ethanol (20 cm3), light petroleum (20 cm3) and dried.
Ϫ1
᎐
Yield: 0.07 g (72%). IR: (CH Cl ) 2098 [ν(C᎐C)], 1918 cm
᎐
2
2
᎐
[ν(CO)]; (Nujol) 2088 [ν(C᎐C)], 1916 [ν(CO)], 1718, 1307, 1263,
᎐
CH ᎐CH , J(AB) = 13.19 Hz], 7.26, 7.74 (m × 2, 30 H, C H );
1216, 1151, 971, 896, 846 and 815 cmϪ1 [δ(C6H4)]. NMR
᎐
α
β
6
5
31P-{1H}, δ 6.59. FAB MS: m/z (%) = 940 (33, [M]ϩ), 905
1
(CDCl3, 25 ЊC): H, δ 2.24 (s, 3 H, CH3), 2.30, 2.40 (s × 2, 3
(44, [M Ϫ Cl]ϩ), 779 (8, [M Ϫ SCCH᎐CHC H Me]ϩ), 648 (7,
᎐
6
4
H × 2, NCH3), 6.49, 6.83 [(AB)2, 4 H, C6H4, J(AB) = 7.92 Hz]
and 7.14–7.92 (m, 30 H, C6H5); 13C-{1H} (CDCl3–CH2Cl2
1:10), δ 209.4 (S2C), 183.4 [t, CO, J(PC) = 9.7], 134.8 [tv, C2,6
(C6H5), J(PC) = 4.9], 133.4 [tv, C1 (C6H5), J(PC) = 24.8], 133.3
[C4 (C6H4)], 130.5 [C2,6 (C6H4)], 129.3 [C4 (C6H5)], 128.1 [C3,5
(C6H4)], 127.2 [tv, C3,5 (C6H5), J(PC) = 4.9], 126.8 [C1 (C6H4)],
[M Ϫ CO Ϫ PPh3]ϩ) and 263 (13, [HPPh3]ϩ) (Found: C, 46.2;
H, 4.5. Calc. for C47H39ClOOsP2Sؒ3CHCl3: C, 46.3; H, 4.3%).
Acknowledgements
᎐
᎐
᎐
α
114.0 (᎐C ), 91.8 [t, ᎐C , J(PC) = 12.9 Hz], 37.2, 36.7 (s × 2,
We are grateful to Johnson Matthey Ltd. for a generous loan of
ruthenium salts. A. F. H. gratefully acknowledges the award
of a Senior Research Fellowship by the Leverhulme Trust and
The Royal Society.
᎐
β
NCH3) and 20.9 (s, CH3); 31P-{1H}, δ 7.2. FAB MS: m/z
(%) = 980 (8, [M]ϩ), 864 (8, [M Ϫ acetylide]ϩ), 830 (6,
[M Ϫ CO Ϫ acetylide]ϩ), 718 (19, [M Ϫ PPh3]ϩ), 691 (12,
[M Ϫ CO Ϫ PPh3]ϩ), 600 (9, [M Ϫ acetylide Ϫ PPh3]ϩ) and 574
(18, [M Ϫ CO Ϫ acetylide Ϫ PPh3]ϩ) (Found: C, 59.9; H, 4.4;
N, 1.3. Calc. for C49H43OOsP2S2: C, 60.2; H, 4.4; N, 1.4%).
References
1 See A. F. Hill, in Comprehensive Organometallic Chemistry II, eds.
E. W. Abel, F. G. A. Stone and G. Wilkinson, Pergamon, Oxford,
1995, vol. 7.
t
᎐
[Os(C᎐CC H Me-4)Cl(CO)(CNBu )(PPh ) ] 15. Complex 13
᎐
6
4
3 2
(0.06 g, 0.06 mmol) was dissolved in dichloromethane (20 cm3)
J. Chem. Soc., Dalton Trans., 1998, 3501–3510
3509

View Article Online
2 L. Vaska, J. Am. Chem. Soc., 1964, 86, 1943.
3 M. R. Torres, A. Vegas, A. Santos and J. Ros, J. Organomet. Chem.,
1986, 309, 169.
4 N. W. Alcock, J. Cartwright, A. F. Hill, M. Marcellin and H. M.
Rawles, J. Chem. Soc., Chem. Commun., 1995, 369.
19 A. F. Hill, M. C. J. Harris and R. P. Melling, Polyhedron, 1992, 11,
781.
20 R. B. Bedford, A. F. Hill, A. R. Thompsett, A. J. P. White and
D. J. Williams, Chem. Commun., 1996, 1059.
21 A. Dobson, D. S. Moore, S. D. Robinson, M. B. Hursthouse and
L. New, Polyhedron, 1985, 4, 1119.
22 A. Dobson, D. S. Moore, S. D. Robinson, M. B. Hursthouse and
L. New, J. Organomet. Chem., 1979, 177, C8.
23 B. E. Cavit, K. R. Grundy and W. R. Roper, J. Chem. Soc., Chem
Commun., 1972, 60.
24 M. Herberhold and A. F. Hill, J. Organomet. Chem., 1989, 377, 151.
25 A. F. Hill and J. D. E. T. Wilton-Ely, Organometallics, 1997, 16,
4517.
26 R. A. Sanchez-Delgado, N. Valencia, R.-L.Marquez-Silva,
A. Andriollo and M. Medina, Inorg. Chem., 1986, 25, 1106.
27 J. Bould, N. N. Greenwood and J. D. Kennedy, J. Organomet.
Chem., 1983, 249, 11.
28 I. D. Burns, A. F. Hill, A. J. P. White, D. J. Williams and J. D. E. T.
Wilton-Ely, Organometallics, 1998, 17, 1552.
29 C. Bohanna, M. A. Esteruelas, A. V. Gomez, A. M. Lopez and
M. P. Martinez, Organometallics, 1997, 16, 4464.
30 A. F. Hill, N. W. Alcock, J. C. Cannadine and G. R. Clark,
J. Organomet. Chem., 1992, 426, C40.
31 A. L. Hector and A. F. Hill, Inorg. Chem., 1995, 34, 3797.
32 N. M. Bell, A. J. Blake, R. M. Christie, R. O. Gould, A. J. Holder,
T. I. Hyde, M. Schröder and L. J. Yellowlees, J. Chem. Soc., Dalton
Trans., 1992, 2977.
33 A. Santos, J. Lopez, A. Galan, J. J. Gonzalez, P. Tinoco and A. M.
Echavarren, Organometallics, 1997, 16, 3482; A. Santos, J. Lopez,
J. Montoya, P. Noheda, A. Romero and A. M. Echavarren, ibid.,
1994, 13, 3605.
34 C. Bohanna, M. A. Esteruelas, J. Herrero, A. M. Lopez and
L. A. Oro, J. Organomet. Chem., 1995, 498, 199; M. A. Esteruelas,
L. A. Oro and N. Ruiz, Organometallics, 1994, 13, 1507.
35 See P. V. Broadhurst, Polyhedron, 1985, 4, 1801.
36 G. R. Clark, T. J. Collins, D. Hall, S. M. James and W. R. Roper,
J. Organomet. Chem., 1977, 141, C5; T. J. Collins and W. R. Roper,
ibid., 1977, 139, C9, C56; 1978, 159, 73.
37 C. E. F. Rickard, W. R. Roper, D. M. Salter and L. J. Wright,
Organometallics, 1992, 11, 3931.
38 G. P. Elliott and W. R. Roper, J. Organomet. Chem., 1983, 250, C5.
39 G. P. Elliott, W. R. Roper and J. M. Waters, J. Chem. Soc., Chem.
Commun., 1982, 811.
5 A. F. Hill and R. P. Melling, J. Organomet. Chem., 1990, 396, C22.
6 J. Montoya, A. Santos, J. Lopez, A. M. Echavarren, J. Ros and
A. Romero, J. Organomet. Chem., 1992, 426, 383; J. Montoya,
A. Santos, A. M. Echavarren and J. Ros, ibid., 1990, 390, C57.
7 A. F. Hill, R. P. Melling and A. R. Thompsett, J. Organomet. Chem.,
1991, 402, C8.
8 N. W. Alcock, A. F. Hill and R. P. Melling, Organometallics, 1991,
10, 3898; A. F. Hill, J. Organomet. Chem., 1990, 395, C35;
J. Cartwright and A. F. Hill, ibid., 1992, 429, 229; J. Cartwright,
A. Harman and A. F. Hill, ibid., 1990, 396, C31.
9 I. D. Burns, A. F. Hill, A. R. Thompsett, N. W. Alcock and K. S.
Claire, J. Organomet. Chem., 1992, 425, C8; N. W. Alcock, I. D.
Burns, K. S. Claire and A. F. Hill, Inorg. Chem., 1992, 31, 4606.
10 J. C. Cannadine, A. F. Hill, A. J. P. White, D. J. Williams and
J. D. E. T. Wilton-Ely, Organometallics, 1996, 15, 5409; J. C.
Cannadine, A. L. Hector and A. F. Hill, Organometallics, 1992, 11,
2323.
11 H. Loumrhari, J. Ros and M. R. Torres, Polyhedron, 1991, 10, 421.
12 A. Romero, A. Santos and A. Vegas, Organometallics, 1988, 7, 1988;
H. Loumrhari, L. Matas, J. Ros, M. R. Torres and A. Perales,
J. Organomet. Chem., 1991, 403, 373; M. R. Torres, A. Perales,
H. Loumrhari and J. Ros, ibid., 1990, 385, 379; H. Loumrhari,
J. Ros, M. R. Torres and A. Perales, Polyhedron, 1990, 9, 907.
13 A. L. Hector and A. F. Hill, J. Organomet. Chem., 1993, 447, C7.
14 N. W. Alcock, A. F. Hill and M. S. Roe, J. Chem. Soc., Dalton Trans.,
1990, 1737.
15 M. C. J. Harris and A. F. Hill, J. Organomet. Chem., 1992, 438, 209;
Organometallics, 1991, 10, 3903.
16 M. A. Esteruelas and H. Werner, J. Organomet. Chem., 1986, 303,
221; H. Werner, M. A. Esteruelas and H. Otto, Organometallics,
1986, 11, 2295; M. A. Esteruelas, E. Sola, L. A. Oro, U. Meyer
and H. Werner, Angew. Chem., Int. Ed. Engl., 1988, 27, 1563;
A. Andriollo, M. A. Esteruelas, U. Meyer, L. A. Oro, R. A.
Sanchez-Delgado, E. Sola, C. Valero and H. Werner, J. Am. Chem.
Soc., 1989, 111, 7431; M. A. Esteruelas, E. Sola, L. A. Oro,
H. Werner and U. Meyer, J. Mol. Catal., 1988, 45, 1; 1989, 53, 43;
H. Werner, U. Meyer, M. A. Esteruelas, E. Sola and L. A. Oro,
J. Organomet. Chem., 1989, 366, 187; H. Werner, M. A. Esteruelas,
U. Meyer and B. Wrackmeyer, Chem. Ber., 1987, 120, 11; V. I.
Bakhmutov, J. Bertran, M. A. Esteruelas, A. Lledos, F. Maseras,
J. Modrego, L. A. Oro and E. Sola, Chem. Eur. J., 1996, 2, 815;
A. Edwards, S. Elipe, M. A. Esteruelas, F. J. Lahoz, L. A. Oro and
C. Valero, Organometallics, 1997, 16, 3828; M. L. Buil, M. A.
Esteruelas, A. M. Lopez and E. Oñate, ibid., 1997, 16, 3169; M. A.
Esteruelas, A. V. Gomez, F. J. Lahoz, A. M. Lopez, E. Oñate and
L. A. Oro, ibid., 1996, 15, 3423; M. A. Esteruelas, A. V. Gomez,
A. M. Lopez and L. A. Oro, ibid., 1996, 15, 878; M. A. Esteruelas,
L. A. Oro and C. Valero, ibid., 1995, 14, 3596; M A. Esteruelas,
F. J. Lahoz, E. Oñate, L. A. Oro and B. Zeier, ibid., 1994, 13, 1662,
4258.
40 G. R. Clark, T. J. Collins, K. Marsden and W. R. Roper,
J. Organomet. Chem., 1978, 157, C23.
41 R. B. Bedford, A. F. Hill, A. J. P. White and D. J. Williams, Angew.
Chem., Int. Ed. Engl., 1996, 35, 95.
42 T. J. Collins, K. R. Grundy and W. R. Roper, J. Organomet. Chem.,
1982, 231, 161.
43 D. J. Cook and A. F. Hill, Chem. Commun., 1997, 955.
44 G. R. Clark, K. Marsden, W. R. Roper and L. J. Wright, J. Am.
Chem. Soc., 1980, 102, 6570.
45 A. F. Hill and J. D. Woollins, in J. D. Woollins (Editor), Inorganic
Experiments, Verlag Chemie, Weinheim, 1994, pp. 225–227.
46 S. Trofimenko, J. Am. Chem. Soc., 1967, 89, 3170.
17 G. J. Irvine, W. R. Roper and L. J. Wright, Abstr. Am. Chem. Soc.,
1997, 213, 674.
18 C. E. F. Rickard, W. R. Roper, G. E. Taylor, J. M. Waters and
L. J. Wright, J. Organomet. Chem., 1990, 389, 375; W. R. Roper and
L. J. Wright, J. Organomet. Chem., 1977, 142, C1.
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