Construction of carbon chains on ruthenium and osmium carbonyl clusters

Article abstract of DOI:10.1016/j.ica.2004.08.027

We have used the elimination of AuX(PR₃) (X = halide, R = Ph, tol) that occurs in reactions of alkynylgold(I)-phosphine complexes with M ₃(μ-H)₃ (μ₃-CBr) (CO)₉ (M = Ru, Os) to prepare the complexes M<

Full text of DOI:10.1016/j.ica.2004.08.027

Inorganica Chimica Acta 358 (2005) 1453–1468
www.elsevier.com/locate/ica
Construction of carbon chains on ruthenium and osmium
carbonyl clusters
a,
a
a
b
Michael I. Bruce *, Paul A. Humphrey , Giovanni Melino , Brian W. Skelton ,
b
Allan H. White , Natasha N. Zaitseva
a
a
Department of Chemistry, University of Adelaide, Adelaide, SA 5005, Australia
Department of Chemistry, University of Western Australia, Crawley, WA 6009, Australia
b
Received 15 July 2004; accepted 11 August 2004
Available online 30 December 2004
Dedicated to Professor F. Gordon A. Stone on the occasion of his 80th birthday, with the greatest respect and admiration
Abstract
We have used the elimination of AuX(PR3) (X = halide, R = Ph, tol) that occurs in reactions of alkynylgold(I)–phosphine com-
plexes with M3(l-H)3(l3-CBr)(CO)9 (M = Ru, Os) to prepare the complexes M3(l-H)3(l3-CC„CR)(CO)9 [M = Ru, R = Ph 2,
C„CSiMe3 3, Fc 4, C„CFc 6-Ru, C„C[Ru(PPh3)2Cp] 8; M = Os, R = C„CFc 6-Os, C„CC„CFc 7], Fc0{(l3-C„CC)Ru3(l-
H)3(CO)9}2 5, and bis-cluster-capped carbon chain complexes {M3(l-H)3(CO)9}2{l3:l3-C(C„C)nC} (M = Ru, n = 2 9, 3 10-Ru;
M = Os, n = 3 10-Os) and {(L)(OC)8(l-H)3M3}C(C„C)nC{Co3(l-dppm)(CO)7} (n = 1, M = Ru, L = CO 11, PPh3 12-Ru/P;
n = 2, L = CO 12-Ru, PPh3 13; M = Os, L = CO 12-Os) in good to excellent yields. X-ray structural determinations of 2–5, 6-Ru,
6-Os, 7, 9, 11, 12-Ru, 12-Os and 12-Ru/P are reported.
ꢀ 2004 Elsevier B.V. All rights reserved.
Keywords: Carbon chains; Ruthenium; Osmium; Capped clusters; Gold elimination
1. Introduction
scribed. Prominent among these are the Co3C clusters
studied by Robinson [9], Seyferth [10] and others.
In previous papers, we have described that reac-
tions between aurated poly-ynes and halo-alkynes re-
sult in a facile elimination of AuX(PR3) (X = halide,
R = Ph, tol) and formation of a new C–C bond [11].
We have used this reaction to make complexes con-
taining long carbon chains (Cn, n > 4), including
{Co3(l-dppm)(CO)7}2{l3:l3-C(C„C)7C} [12]. The
reactions are carried out in ether solvents (Et2O, thf)
at moderate temperatures in the presence of a Pd(0)/
Cu(I) catalyst, and generally proceed in excellent yield.
Other studies in our laboratory have shown that this
reaction, which may be considered to be a variant of
the well-known Sonogashira reaction [13], has wide
applicability. The AuX(PR3) product may be recov-
ered and re-used.
Current interest in metal complexes which may be
considered to be models of molecular wires includes a
vigorous sub-set comprised of carbon chains end-capped
by redox-active metal–ligand fragments [1]. Several
groups have concentrated on derivatives containing
mononuclear fragments, such as MnX(dmpe)2 (X = I,
C„CH) [2], Re(NO)(PPh )Cp [3], Fe(CO) Cp [4],
*
*
3
2
Fe(dppe)Cp [5], Ru(L)2Cp0 (L = PPh3, Cp0 = Cp,
*
L = dppe, Cp0 = Cp ) [6] and Pt(C F )(PR ) [7], or
*
2
6
5
3 2
the binuclear Ru2(ap)4 (ap = 2-anilinopyridinate) system
[8]. However, relatively few examples of analogous com-
plexes containing metal cluster moieties have been de-
*
Corresponding author. Tel.: +618 8303 5939; fax: +618 8303 4358.
E-mail address: michael.bruce@adelaide.edu.au (M.I. Bruce).
0020-1693/$ - see front matter ꢀ 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.ica.2004.08.027

1454
M.I. Bruce et al. / Inorganica Chimica Acta 358 (2005) 1453–1468
Part of our studies of molecules which contain a car-
LnM
(C
C)m MLn
bon chain linking two metal centres has been concerned
with the electronic communication between the end-caps
and we have been interested to examine compounds in
which one or two metal cluster moieties cap the chain.
Of these, some contain the metal cluster bonding via
three metal atoms to a C(sp) atom, the C(1)–C(2) dis-
tance being of the same order as that expected for a
CC triple bond. An example is [M3(l3-CCBut)2(l-
dppm)3]+ (M = Cu, Ag) [14,15]. The clusters here usu-
ally contain Group 11 atoms (Cu, Ag). Other cluster
carbyne systems are also known, in which the cluster-
bonded carbon C(1) also interacts with three metal
atoms, but is only singly bonded to C(2). Examples in-
clude the well-established Co3(l3-CX)(CO)9 [9,10] and
related complexes of the Group 8 metals, M3(l-H)3(l3-
CX)(CO)9 (M = Ru, Os) [16,17]. In principle, many
other cluster cores can be obtained by conventional me-
tal-exchange reactions. This paper describes some car-
bon-chain complexes in which one end-cap is the
M3(l-H)3(CO)9 (M = Ru, Os) group which have been
prepared by the general reaction shown in Eq. (1).
A
LnM
(C
C)m MLn
B
LnM
(C
C)m MLn
C
LnM (C
C)m
C
C
M'L'n
M'L'n
D
LnM (C
C)m
E
Chart 1.
(CO)3
M
H
2. Results
H
C
Br
(Ph3P)Au
+
C
C
R
(OC)3M
H
The halo-carbyne complexes M3(l-H)3(l3-CX)(CO)9
(M = Ru, Os, X = Cl, Br, I) were originally described
by Shapley [17] and are readily available from the parent
M3(CO)12 by sequential treatment with NEt3 [or more
recently, with (MeNCH2)3], MeOTf and then BX3
[19,20]. Reactions of these complexes with aurated alky-
nes have given the 16 complexes to be described below in
good to excellent yield. All have been characterized by
satisfactory elemental analyses, appropriate spectro-
scopic properties and in 12 cases, by single-crystal X-
ray structure determinations.
M
(CO)3
(CO)3
M
H
H
AuBr(PPh3)
R
+
C
C
C
(OC)3M
H
M
(CO)3
ð1Þ
The electronic nature of carbon chains is of interest
in connection with their possible use as molecular
wires. For chains containing an even number of carbon
atoms, three symmetrical electronic configurations are
possible (neglecting radical species), as indicated by
structures A–C in Chart 1 [1]. This type of complex
is the most prevalent, because of the use of mono- or
poly-yne precursors in their syntheses. For odd-num-
bered chains, only two representations are possible,
namely D and E. The former is related to B, and both
involve at least one M–C multiply-bonded linkage.
Possible precursors of the odd (single) carbon atom,
which might be linked to an even-numbered chain from
another source, include metal carbyne complexes.
The reaction between equimolar amounts of Ru3(l-
H)3(l3-CBr)(CO)9 (1-Ru) and Au(C„CPh)(PPh3) was
carried out in thf at r.t. with added Pd(PPh3)4 and CuI
as catalyst and afforded yellow-orange crystals of
Ru3(l-H)3(l3-CC„CPh)(CO)9 (2) in 74% yield. Similar
reactions were carried out with the copper and silver
analogues of the gold alkynyl and gave 2 in 75% and
32% yields, respectively; unreacted 1-Ru (42%) was
recovered from the silver reaction. The IR spectrum of
2 contained a m(C„C) band at 2110 cmꢀ1 and terminal
m(CO) bands between 2084 and 1991 cmꢀ1, the vs–vs–s–s
pattern of which is characteristic of the Ru3(l-H)3(CO)9
1
These contain M„C bonds, as in W(„CR)(CO) Tp
fragment. The H NMR spectrum contains two reso-
*
2
[18], or a carbon l3-bonded to a trinuclear cluster, as
in the Co3(l3-CR)(CO)9 complexes mentioned above.
Several other systems are known and, in addition to
some Co3C systems, we have chosen to study the
Group 8 clusters M3(l-H)3(l3-CX)(CO)9 (M = Ru, Os)
as precursors.
nances at d ꢀ17.64 (Ru–H) and between 7.20 and 7.39
(Ph), while the 13C NMR spectrum contains, in addition
to signals between d 126.9 and 130.8 (Ph) and at d 188.9
and 189.8 (CO), three singlets at d 93.1, 110.1 and 156.4,
which are assigned to the three carbons of the C3 chain.
In 1-Ru and 1-Os, the cluster-bonded carbons resonate

M.I. Bruce et al. / Inorganica Chimica Acta 358 (2005) 1453–1468
1455
at d 187.1 and 124.1, respectively [21], while the two car-
bons of HC„CPh are found at d 77.1 and 83.4 [22]. The
electrospray mass spectrum (ES-MS), run in the pres-
ence of NaOMe, contained ions at m/z 673 and 703, as-
signed to Mꢀ and [M + OMe ꢀ H]+, respectively.
Extension to a C5 chain was readily achieved by using
suitable diynyl-gold precursors. Thus, the reaction be-
tween Me3SiC„CC„CAu(PPh3) [23] and 1-Ru affor-
ded orange Ru3(l-H)3(l3-CC„CC„CSiMe3)(CO)9 (3)
in 88% yield. Only one m(C„C) absorption is found in
the IR spectrum, together with the m(CO) peaks for
the cluster carbonyl. The characteristic resonances of the
SiMe3 group were found at dH 0.24 and dC 0.1 in the
1H and 13C NMR spectra, respectively, while [M ꢀ H]ꢀ
at m/z 692 in the negative ion ES-MS, together with a
single-crystal X-ray structure determination, also served
to confirm its identity.
(C5H4) and 70.0 (Cp) (for 6-Os), and at d 65.6 (ipso),
69.5 and 72.4 (C5H4) and 70.3 (Cp) (for 7). The carbons
of the C7 chain are found between d 63.3 and 102.3. The
ES-MS show the anticipated [M + OMe]ꢀ ions at m/z
1103 and 1127, respectively, while the spectrum of 6-
Os also contains the ions [M ꢀ H ꢀ nCO]ꢀ (n = 0–4)
at m/z 1071–959.
We explored the possibility of linking the redox-ac-
tive Ru(PPh3)2Cp group to the Ru3 cluster by carrying
out
Ru{C„CC„CAu[P(tol)3]}(PPh3)2Cp. The complex
Ru3(l-H)3{l3-CC„CC„C[Ru(PPh3)2Cp]}(CO)9 (8)
a
reaction
between
1-Ru
and
was obtained in essentially quantitative yield as an or-
ange solid whose IR spectrum contains only the stron-
gest of the expected m(CO) bands.
Reactions between 1 and digold poly-yne compounds
have given symmetrical bis-clusters in which the Cn
chain is end-capped by two cluster moieties. Thus, 1-
Ru reacted with {Au[P(tol)3]}2{l-(C„C)2} to give red
{Ru3(l-H)3(CO)9}2{l3:l3-C(C„C)2C} (9). The IR
spectrum contained m(C„C) bands at 2128 and 2106
cmꢀ1 together with the characteristic m(CO) pattern.
The ferrocenyl group is a well-known redox-active
group and we sought to make compounds containing
the M3 clusters linked to a ferrocene moiety by carbon
chains of various lengths. Accordingly, we found that
1-Ru reacts with Au(C„CFc)(PPh3) to give orange
Ru3(l-H)3(l3-CC„CFc)(CO)9 (4) in 66% yield. Again,
one m(C„C) band is found in the IR spectrum at 2108
1
The H NMR spectrum contains the RuH resonance
at d ꢀ17.66, but we have not yet managed to obtain a
useful 13C NMR spectrum. The ES-MS spectra shows
[M ꢀ H]ꢀ at m/z 1189, while solutions containing
NaOMe had [M + OMe]ꢀ at m/z 1221.
1
cmꢀ1, together with the usual m(CO) bands. In the H
NMR spectrum, the RuH resonance is found at d
ꢀ17.55 and resonances for the Cp and C5H4 protons
are at d 4.21, and 4.20 and 4.40, respectively. In the
13C NMR spectrum, four signals in a 1/2/2/5 ratio are
found at d 67.9, 68.6, 70.9 and 69.6, which are readily
assigned to the ipso and other ring C of the C5H4 group
and the Cp carbons, respectively. Both positive- and
negative-ion ES-MS contain M ions at m/z 781.
Both 1-Ru and 1-Os underwent similar reactions with
{Au[P(tol)3]}2{l-(C„C)3} to give the novel C8-bridged
cluster complexes {M3(l-H)3(CO)9}{l3:l3-C(C„C)3C}
[10-Ru (orange) and 10-Os (red-orange), respectively].
Their spectroscopic properties are virtually identical,
showing m(C„C) bands at 2133 and 2107 (Ru) or
2112 cmꢀ1 (Os) and MH resonances at d ꢀ17.85 (Ru)
and ꢀ19.05 (Os). In the ES-MS spectra, 10-Ru shows
[M + OMe]ꢀ at m/z 1245, while for 10-Os, this ion is
found at m/z 1779.
Complexes containing C4 or C6 chains linking two
dissimilar clusters have also been obtained. The reac-
tions between 1-Ru and Co3{l3-C(C„C)nAu(PPh3)}-
(l-dppm)(CO)7 (n = 2, 3) have given the corresponding
derivatives {(OC)9(l-H)3Ru3}{l3: l3-C(C„C)nC}-
{Co3(l-dppm)(CO)7} (n = 2 11, 3 12-Ru) together with
small amounts of the related PPh3 complexes {(Ph3P)-
(OC)8(l-H)3Ru3}{l3:l3-C(C„C)nC}{Co3(l-dppm)(CO)7}
(n = 2 11-P, 3 12-Ru/P). The analogous reaction be-
tween 1-Os and Co3{l3-C(C„C)2Au(PPh3)}(l-dppm)
(CO)7 afforded {(OC)9(l-H)3Os3}{l3:l3-C(C„C)2C}
{Co3(l-dppm)(CO)7} (12-Os) in 79% yield, no PPh3-
substitution product being identified in this case. These
complexes were characterised from their spectroscopic
properties and, in the cases of 11, 12-Ru and 12-Ru/P,
by single-crystal X-ray structure determinations (see
below). The IR spectra contained many m(CO) bands,
the pattern of which approximated to a superposition
of those of the two cluster carbonyl moieties.
An analogous reaction between 1-Ru and
Fc0{C„CAu[P(tol)3]}2 [Fc0 = 1,10-ferrocenylene, Fe(g-
C5H4–)2] afforded the corresponding orange bis-cluster
derivative Fc0{(l3-C„CC)Ru3(l-H)3(CO)9}2 (5) in
23% yield. Spectroscopic properties of 5 are similar to
those of 4, with m(C„C) at 2109 cmꢀ1 and the familiar
1
m(CO) pattern. In the H NMR spectrum, the RuH res-
onance is at d ꢀ17.61, while the Cp singlet of 4 is absent.
In the ES-MS spectrum, Mꢀ is found at m/z 1374.
Derivatives with longer carbon chains were also pre-
pared using both 1-Ru and the triosmium cluster 1-Os
for variety. Thus, Au(C„CC„CFc)(PPh3) and 1-Ru
afforded red-orange Ru3(l-H)3{l3-C(C„C)2Fc} (6-
Ru), while Au{(C„C)nFc}(PPh3) (n = 2, 3) and 1-Os
afforded red-orange Os3(l-H)3{l3-C(C„C)nFc} (n = 2
6-Os, 3 7). All complexes showed only one m(C„C)
band in their IR spectra, while the m(CO) patterns of 6
were simpler (three or six bands) than that of 7 (seven
bands). The NMR parameters were very similar, with
the Ru–H resonance in 6-Ru at d ꢀ17.78 and the OsH
resonances at d ꢀ19.03 (6-Os) and ꢀ19.09 (7) and the
Fc protons being similarly almost indistinguishable.
The Fc carbons resonate at d 65.2 (ipso), 68.9 and 71.8

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M.I. Bruce et al. / Inorganica Chimica Acta 358 (2005) 1453–1468
Single m(C„C) bands were present at ca 2100 cmꢀ1. In
the NMR spectra, the characteristic MH resonances
appeared at dH ca ꢀ 17.5(Ru) and d ꢀ18.8 (Os).
The ES-MS of solutions in MeOH containing NaOMe
contained [M + OMe]ꢀ ions at m/z 1396 (11),
1420 (12-Ru), 1687 (12-Os), 1630 (11-P) and 1654 (12-
Ru/P).
The PPh3-containing complexes 11-P and 12-Ru/P
were probably formed by abstraction of PPh3 from
the AuBr(PPh3) by-product, although these were the
13C NMR and bond lengths within Cn chains
{Ru3}
C1
C1
C1
C2
C3
93.1
Ph
156.4
110.1
(2)
1.410(3) 1.211(4) 1.423(4)
{Ru3}
C2
C3
92.4
Fc
158.6
106.2
(4)
1.423(3) 1.194(4) 1.422(4)
{Ru3}
C2
C3
Fc'
1.411(7) 1.216(7) 1.423(7)
(5)
{Ru3}
C1
C2
C3
94.4
C4
89.3
C5
SiMe3
1.833(3)
148.9
96.6
(3)
1.393(3) 1.219(3) 1.371(3)
1.205(4)
{M3}
C1
-
C2
C3
C4
77.8
C5
Fc
99.1
86.5
71.6
(6-Ru)
1.403(8) 1.204(8) 1.382(8) 1.203(8)
1.423(8)
69.6
1.216(9) 1.420(9)
103.1
1.392(9) 1.225(9) 1.355(9)
99.0
81.0
71.9
(6-Os)
{Os3}
C1
102.3
C2
C3
C4
71.9
C5
C6
C7
Fc
102.0
78.8
69.1
66.8
63.3
(7)
1.400(8) 1.233(8) 1.350(9)
1.219(9) 1.365(9) 1.213(9) 1.414(8)
C4
{Co3}
1.398(3) 1.232(3) 1.381(3)
{Ru3}
C1
C2
C3
(11)
{M3}
(12-Ru)
C1
C2
C3
C4
C5
C6
{Co3}
109.4
97.6
116.6
79.2
1.44(3)
1.46(3)
1.19(3)
1.39(3)
1.15(4)
121.1
1.44(3) 1.21(3)
103.9
98.9
71.5
(12-Os)
1.39(3) 1.17(3)
1.41(3)
{P-Ru3}
(12-P)
C1
C2
C3
C4
C5
1.204(0)
C6
1.380(0)
{Co3}
1.388(0) 1.210(0) 1.376(0)
Chart 2.

M.I. Bruce et al. / Inorganica Chimica Acta 358 (2005) 1453–1468
1457
only occasions in which such products were isolated.
The identities of these complexes was revealed from
elemental analyses and their ES-MS, and confirmed
from the 31P NMR spectra which showed the presence
of both PPh3 and dppm resonances at d 27.66 and
33.88 (11-P) and 28.26 and 34.62 (12-Ru/P). The 1H
NMR spectra each contain two Ru–H resonances
(intensity ratio 2/1), which are assigned to the H atoms
bridging the two Ru(PPh3)–Ru(CO) bonds and to the
gard, it is unfortunate that we were unable to fully re-
solve the spectrum of complexes 11 and 12, which
would perhaps have given confirmatory evidence.
3. Molecular structures
In the course of this work, the molecular structures of
12 of these complexes have been determined by single-
crystal X-ray diffraction studies. Plots of the individual
molecules are presented in Figs. 1–3 and selected struc-
tural parameters are collected in Tables 1 and 2. The fol-
lowing discussion of the structures does not include any
quantitative data from 12-Ru, which determination is
rather less precise than the other eleven. All contain at
least one M3(l-H)3(CO)8(L) (M = Ru, Os, L = CO,
PPh3) cluster attached to the end carbon of the Cn chain
by a l3-g1 interaction. Although the M3(l-H)3(CO)9
clusters are symmetrically attached to this atom, depar-
tures from exact symmetry in the cluster are widespread,
with unequal M–M distances ranging between 2.831(3)
H
atom bridging the Ru(CO)3–Ru(CO)3 bonds,
respectively.
Of interest are the 13C resonances found for the
atoms in the Cn chains. While not all have been success-
fully resolved on account of the low solubility of some of
these complexes, we have been able to assign the reso-
nances listed in Chart 2. These C(sp) atoms do not bear
any other substituents, so do not relax readily, leading
to low relative intensities which, however, all have
approximately equal intensities. Previous studies have
been in general agreement that carbons attached to the
transition metal(s) appear downfield of those in the cen-
tre of the chain and those bearing other substituents [1].
Assignments of resonances to individual carbons (in the
absence of useful coupling to other nuclei such as 31P)
have generally followed a rule of thumb by which the
chemical shift decreases as one moves away from the
metal substituent. We are cognisant of the assignment
of the cluster-bonded carbon in CCo3 clusters to a signal
at relatively high chemical shift (which is also broadened
by the Co quadrupole moment and therefore not often
observed). In the present cases, however, we are guided
by the chemical shift of the cluster-bonded C(sp) atom
in precursor 1-Ru, which is found at d 187.1. In this re-
˚
˚
and 2.8560(3) A [av. 2.846 A](Ru) and between
˚
2.8694(4) and 2.8926(4) A [av. 2.883 A](Os), and M–C
˚
˚
distances between 2.082(2) and 2.11(3) A(Ru) and be-
˚
˚
tween 2.099(6) and 2.126(5) A [both av. 2.088 A](Os).
The M–CO distances fall into two ranges: 1.895(3)–
˚
1.924(3) and 1.972–1.993(3) A (Ru) and 1.901(8)–
˚
1.924(8) and 1.957–1.981(6) A (Os), which readily
distinguish the shorter equatorial CO groups from the
longer axial groups. The PPh3 ligand in 12-Ru/P occu-
˚
pies an equatorial site with Ru–P 2.395(2) A, the Ru–C
and Ru–CO distances falling within the ranges men-
tioned above.
(CO)3
M
(CO)3
Ru
H
H
H
H
C
C
C
C
C
R
(OC)3M
H
C
C
C
R
(OC)3Ru
H
M
Ru
(CO)3
(CO)3
R = Ph (2), Fc (4)
M = Ru, R = SiMe3 (3), Fc (6-Ru),
Ru(PPh3)2Cp (8)
M = Os, R = Fc (6-Os)
(CO)3
Ru
H
(OC)3Ru
H
H
C
C
C
(CO)3
Ru
Fe
Ru
H
(CO)3
H
C
C
C
Ru(CO)3
H
Ru
(CO)3
(5)

1458
M.I. Bruce et al. / Inorganica Chimica Acta 358 (2005) 1453–1468
The three H atoms which bridge the three Ru–Ru
1
vectors, revealed in the H NMR spectra, were located
there is a general shortening towards the center of
the chain. This is shown in the structures of 6 and
7, where the C(sp)–C(sp) separations are 1.382(8)
(for 6-Ru) and 1.355(9) (6-Os), and 1.350(9) and
during the refinements of 2–5, 9, 11 and 12-Ru/P and
are on the opposite side of the Ru3 core from the l3-C
atom. The refined Ru–H separations range between
˚
1.365(9) A (for 7), the first value for 7 being the short-
est found in all these structures. The C–C separations
involving the cluster-bonded carbons fall in the range
˚
˚
1.68 and 1.92(4) A(av. 1.78 A). There appears to be no
consistent reason for the differences in individual Ru–
H distances.
˚
1.388(0) to 1.423(3) A [neglecting the more imprecise
˚
value of 1.46(3) A found for 12-Ru]. These features
The CCo3 clusters in 11, 12-Ru, 12-Os and 12-Ru/P
each bear a dppm ligand bridging the Co(4)–Co(5)
˚
vector [Co–P 2.1832(6)–2.203(6) A], with the P atoms
have also been noted in a recent more general survey
of the properties of carbon chains in molecules of the
type discussed here [24].
occupying equatorial sites. The Co–Co distances are
not affected by the presence of the dppm ligand [ranges
˚
Comparisons with the structures of Co3(l3-C„CR)
(CO)9 (R = SiMe3, Fc, C„CSiMe3) [25] reveal similar
Co–Co and Co–C(1) distances, with no evidence for
distortion of the CCo3 cluster. The C–C bond lengths
also show an alternation along the chain, consistent
with the presence of C–C single and C„C triple bonds,
with values similar to those found in the present stud-
ies. The shortening of the central C–C bond in the diy-
nyl complex is also found here and again is consistent
with a degree of conjugation along the poly-yne chain.
The cluster C(carbyne)–C(2) bonds are also short as
expected for single bonds linking two C(sp) carbon
atoms, although in these three complexes, the separa-
2.464(5)–2.4893(5)
˚
A
2.480(1) A for Co(4,5)–Co(6). In contrast, the Co–C
for Co(4)–Co(5), 2.462(4)–
distances are shorter from Co(4) and Co(5) [1.906(2)–
˚
˚
1.92(2) A] than from Co(6) [1.939(7)–1.956(2) A], in
keeping with the asymmetry consequent upon the
coordination of the dppm. Again, the axial Co–CO
˚
distances are somewhat longer [1.821(3)–1.88(3) A]
than the equatorial Co–CO distances [1.74(3)–
˚
1.803(3) A].
(CO)3
M
(CO)3
M
H
(OC)3M
H
H
˚
tions are shorter [1.37(2)–1.388(7) A]. These are similar
to those found for the C„{Co3} clusters in 11 and 12-
H
H
C
(C C)n
C
M(CO)3
˚
Ru/P, but shorter than the 1.44(3) A in 12/Ru. Further
H
M
M
comparisons can be made with the bis-cluster com-
plexes {Co3(CO)9}2(l3:l3-CC„CC) [with C(1)–C(2)
(CO)3
(CO)3
0
˚
and C(2)–C(2 ) being 1.24(2) and 1.37(1) A, respec-
Ru
Ru
Os
2
3
3
9
tively] [26] and {(Me3SiC)Co3Cp3}2(l3:l3-CC
„CC„CC), in which the C–C separations along the
C6 chain are 1.43(3), 1.18(2), 1.36(2), 1.21(2) and
10-Ru
10-Os
˚
1.44(2) A [27].
(CO)2(L)
M
(CO)3
Co
H
Angles at individual carbon atoms within the chains
range between 167.5(2.8)ꢁ and 179.8(2)ꢁ, the only corre-
lation being that the minimum bending appears to be at
the central carbon(s) of the chain. As a recent review has
commented, there seem to be no rationalisations of these
distortions with electronic or steric factors, the most
likely explanation being ‘‘crystal packing forces’’ allied
with a small bending force constant of the C(sp)–C(sp)
bond [25].
H
(OC)3M
C
(C C)n
C
Co(CO)2
PPh2
H
M
(OC)2Co
(CO)3
Ph2P
Ru
CO
PPh3
CO
CO
PPh3
1
1
2
2
2
11
Ru
Ru
Os
Ru
11-P
12-Ru
12-Os
12-Ru/P
A brief comparison of the isomorphous and iso-
structural ruthenium/osmium pairs 6-Ru/6-Os and 12-
Ru/12-Os shows little difference in the volume of the
3
˚
unit cell [Z = 2, 1300/1293 A (6) and Z = 4, 5566/
3
5590 A (12)]. The average M–M bond lengths are
˚
Of most interest are the separations between the
carbon atoms in the Cn chains. In all cases, the
. . . long–short–long– . . . sequence is preserved, which
can be interpreted in terms of conjugated C„C triple
bond systems attached to the cluster-bonded car-
bon(s). The ranges are 1.194(4)–1.232(3) and
˚
2.856, 2.885 (6) and 2.842, 2.883 A(12), showing a dif-
˚
ference of 0.029, 0.041 A; the average M–C(1) bond
˚
lengths are 2.096, 2.118 (6) and 2.09, 2.13 A(12), giving
˚
differences of 0.022, 0.04 A, respectively. These data
may be compared with those determined for
˚
˚
M3(CO)12, which have M–M (av.) 2.854, 2.877 A with
˚
a difference of 0.023 A.
1.350(9)–1.423(3) A, for the short and long separa-
tions, respectively, although as shown in Chart 2,

M.I. Bruce et al. / Inorganica Chimica Acta 358 (2005) 1453–1468
1459
(a)
(b)
302
502
503
501
Si
301
5
4
3
2
CO(33)
3
CO(32)
1
2
CO(33)
CO(13)
CO(12)
CO(23)
CO(32)
CO(13)
CO(22)
1
CO(22)
Ru(2)
CO(12)
CO(23)
Ru(2)
Ru(1)
Ru(3)
Ru(1)
CO(21)
1
CO(1 )
CO(31)
CO(11)
CO(21)
CO(31)
(c)
(d)
304’
304
305
CO(32)
305’
301’
303
Fe
303’
CO(12)
Ru(3)
Ru(2)
302
302’
CO(33)
301
CO(31)
1
302
Ru(1)
2
303
304
3
3
CO(13)
CO(21)
301
305
Fe
2
CO(32)
CO(11)
CO(22)
CO(23)
CO(33)
CO(13)
1
CO(22)
CO(23)
CO(12)
Ru(1)
Ru(2)
CO(21)
CO(11)
CO(31)
Fig. 1. Molecular projections of: (a) 2, (b) 3, (c) 4 and (d) 5.
4. Conclusions
(n = 3–8) to various other functional groups or clusters.
X-ray structural studies have shown that there is little or
no delocalisation of p electrons along the chain, the
familiar long–short–long sequence of bond lengths indi-
cating the preservation of the conjugated –C„C–C„
systems.
The work here has extended the scope of our novel
phosphine–gold(I) halide elimination reaction to deriva-
tives containing the M3(l-H)3(CO)8(L) clusters
(M = Ru, Os; L = CO, PPh3) linked via Cn chains

1460
M.I. Bruce et al. / Inorganica Chimica Acta 358 (2005) 1453–1468
CO(33)
CO(31)
505’
501’
504’
CO(32)
CO(12)
Os(3)
Os(1)
Os(2)
502’
503’
Fe
2
3
1
4
5
505
502
501
504
CO(13)
CO(23)
CO(21)
503
CO(11)
CO(22)
(a)
704’
705’
703
702’
Fe
701’
CO(33)
704
CO(31)
CO(12)
705
703
7
CO(32)
Os(3)
6
701
702
5
CO(13)
4
3
1
2
Os(1)
Os(2)
CO(21)
CO(22)
CO(23)
CO(11)
(b)
Fig. 2. Molecular projections of: (a) 6-Os (6-Ru is similar) and (b) 7.
5. Experimental
121.503 MHz) or 600 Unity Nova (1H at 599.92 MHz)
instruments. Samples were dissolved in CDCl3, unless
otherwise stated, contained in 5 mm sample tubes. Chem-
ical shifts are given in ppm relative to internal tetrameth-
ylsilane for 1H and 13C NMR spectra and external H3PO4
for 31P NMR spectra. ES mass spectra: A VG Platform 2
instrument was used, solutions in MeOH being directly
infused into the instrument. Chemical aids to ionisation
were used as required [28]. Elemental analyses were per-
formed at CMAS, Melbourne, Australia.
5.1. General experimental conditions
All reactions were carried out under dry, high purity
argon using standard Schlenk techniques. Common sol-
vents were dried, distilled under argon and degassed be-
fore use.
5.2. Instrumentation
Infrared spectra were obtained on a Bruker IFS28 FT-
IR spectrometer. Spectra in CH2Cl2 were obtained using
a 0.5 mm path-length solution cell with NaCl windows.
NMR spectra were recorded on Bruker AM300WB,
ACP300 (1H at 300.13 MHz, 13C at 75.47 MHz, 31P at
5.3. Reagents
The compounds M3(l-H)3(l-CBr)(CO)9 (M = Ru,
Os) [19], Au(C„CR)(PR3) (R = Ph [29], Fc [30],
C„CSiMe3 [23], (C„C)nFc (n = 1, 2) [31] ; R0 = Ph,

M.I. Bruce et al. / Inorganica Chimica Acta 358 (2005) 1453–1468
1461
CO(13)
CO(33)
CO(52)
CO(11)
Ru1
CO(21)
CO(22)
CO(23)
511
P(5)
Co(5)
512
3
CO(12)
CO(51)
Ru(2)
Ru3
CO(63)
4
3
2
1
CO(33)
2
521
CO(31)
522
CO(61)
CO(41)
CO(31)
1
Co(6)
CO(22)
Ru2
Co(4)
CO(13)
CO(32)
CO(32)
CO(23)
CO(62)
CO(21)
Ru(1)
422
P(4)
421
CO(42)
411
CO(11)
CO(12)
412
(a)
(b)
CO(22)
CO(52)
521
511
CO(21)
512
1412
CO(33)
CO(23)
CO(133)
1422
1511
1521
1421
Ru(2)
1522
CO(63)
5
CO(51)
CO(132)
10
Co(5)
CO(31)
10
4
1411
15
1
2
3
P(15)
CO(131)
CO(61)
P(14)
6
Co(6)
Co(4)
122
132
131
Co(15)
Co(14)
Co(16)
P(4)
CO(62)
CO(141)
CO(152)
CO(32)
CO(122)
11
Os(13)
13
12
14
Ru(1)
426
CO(151)
CO(161)
CO(41)
CO(13)
CO(12)
16
Os(12)
P(1)
111
411
CO(42)
CO(142)
CO(112)
CO(123)
111’
CO(121)
412
112’
Os(11)
112
CO(163)
CO(162)
CO(111)
CO(113)
(c)
(d)
Fig. 3. Molecular projections of: (a) 9, (b) 11, (c) 12-Os (12-Ru is similar) and (d) 12-Ru/P.
tol [26]), {Au(PR3)}2{l-(C„C)n} (n = 2, 3) [12],
Cu(C„CPh)(PPh3) [32] and Ag(C„CPh)(PPh3) [33]
were prepared using the cited methods or slight modifi-
cations thereof.
189.8 (2 · s, CO). ES-MS (negative ion, MeOH +
NaOMe, m/z): 673, Mꢀ, 703, [M + OMe ꢀ H]ꢀ.
5.4.2. With Cu(C„CPh)(PPh3)
Similarly, a reaction between 1-Ru (24 mg, 0.037
mmol) and Cu(C„CPh)(PPh3) (16 mg, 0.037 mmol) in
the presence of Pd(PPh3)4 (2 mg, 0.002 mmol) and CuI
(1.0 mg, 0.005 mmol) in thf (8 ml) afforded 2 (18 mg, 75%).
5.4. Reactions of Ru3(l-H)3(l3-CBr)(CO)9 (1-Ru)
5.4.1. With Au(C„CPh)(PPh3)
Pd(PPh3)4 (4.2 mg, 0.0036 mmol) and CuI (1.0 mg,
0.005 mmol) were added to a solution of Ru3(l-H)3(l3-
CBr)(CO)9 (1-Ru) (53 mg, 0.082 mmol) and
Au(C„CPh)(PPh3) (46 mg, 0.082 mmol) in thf (8 ml).
After stirring at r.t. for 1.5 h and evaporation to dryness
(rotary evaporator), preparative t.l.c. (hexane–acetone
4/1) of the residue gave a major orange-yellow band (Rf
0.89) containing Ru3(l-H)3(l3-CC„CPh)(CO)9 (2) (41
mg, 74%), which formed yellow-orange crystals
(CH2Cl2/MeOH). Anal. Calc. for (C18H8O9Ru3): C,
32.20; H, 1.20. Found: C, 32.24; H, 1.18%. M, 673. IR
(CH2Cl2): m(C„C) 2110w; m(CO) 2084vs, 2035vs, 2026
5.4.3. With Ag(C„CPh)(PPh3)
From 1-Ru (31 mg, 0.048 mmol) and
Ag(C„CPh)(PPh3) (22 mg, 0.047 mmol) in the presence
of Pd(PPh3)4 (2.8 mg, 0.002 mmol) and CuI (1.0 mg,
0.005 mmol) in thf (6 ml) was obtained 2 (10 mg,
32%), together with recovered 1-Ru (13 mg, 42%).
5.4.4. With Au(C„CC„CSiMe3)(PPh3)
Addition of thf (10 ml) to a mixture of 1-Ru (27 mg,
0.041 mmol) and Au(C„CC„CSiMe3)(PPh3) (24 mg,
0.041 mmol), Pd(PPh3)4 (2 mg, 0.002 mmol) and CuI (1
mg, 0.005 mmol) and stirring for 2 h gave, after prepara-
tive t.l.c. (hexane–acetone 3/1) a yellow band (Rf 0.86)
1
(sh), 1991 (sh) cmꢀ1. H NMR: d ꢀ17.64 (s, 3H, RuH),
7.20–7.39 (m, 5H, Ph). 13C NMR: d 93.1, 110.1, 156.4
(3 · s, C3 chain), 126.9, 128.3, 130.8 (3 · s, Ph), 188.9,

Table 1
Bond parameters for 2-5, 6-Ru, 6-Os, 7 and 9 (core M–H included, where refined)
2
3
4
5
6-Ru
6-Os
7
9
˚
Bond distances (A)
M(1)–M(2)
M(1)–M(3)
M(2)–M(3)
M(1)–C(1)
M(2)–C(1)
M(3)–C(1)
C(1)–C(2)
2.8560(3)
2.8384(3)
2.8447(3)
2.092(2)
2.097(2)
2.082(2)
1.410(3)
1.211(4)
2.8468(3)
2.8465(3)
2.8496(3)
2.086(2)
2.8448(3)
2.8491(3)
2.8508(3)
2.085(2)
2.086(2)
2.092(2)
1.423(3)
1.194(4)
2.8526(6)
2.8437(4)
2.8479(5)
2.089(4)
2.104(5)
2.087(4)
1.411(7)
1.216(7)
2.8550(6)
2.8503(5)
2.8613(5)
2.089(4)
2.8857(3)
2.8795(3)
2.8885(3)
2.117(5)
2.8803(4)
2.8926(4)
2.8694(4)
2.122(7)
2.8500(3)
2.8465(3)
2.8488(3)
2.092(2)
2.088(2)
2.090(2)
2.106(5)
2.093(5)
2.126(5)
2.112(5)
2.099(6)
2.121(6)
2.083(2)
2.092(2)
1.393(3)
1.219(3)
1.403(8)
1.204(8)
1.392(9)
1.225(9)
1.400(8)
1.223(8)
1.398(3)
1.216(3)
1.361(3) [C(30)]
C(2)–C(3)
C(3)–C(4)
1.371(3)
1.205(4)
1.382(8)
1.203(8)
1.355(9)
1.216(9)
1.350(9)
1.219(9)
C(4)–C(5)
C(n)–C(n01) [n]
M(1)–CO(1n)
1.423(4) [3]
1.972, 1.913,
1.905(3)
1.833(3) [5; Si]
1.983, 1.923,
1.916(3)
1.422(4) [3]
1.986, 1.914,
1.916(4)
1.423(7) [3]
1.904, 1.908,
1.986(6)
1.423(8) [5]
1.910, 1.915,
1.993(6)
1.420(9) [5]
1.916, 1.919,
1.981(6)
1.414(8) [7]
1.901, 1.924,
1.966(8)
1.981, 1.912,
1.910(3)
M(2)–CO(2n)
M(3)–CO(3n)
1.978, 1.909,
1.924(3)
1.976, 1.910,
1.909(3)
1.993, 1.912,
1.912(3)
1.907, 1.914,
1.976(6)
1.917, 1.923,
1.968(7)
1.919, 1.915,
1.950(6)
1.924, 1.911,
1.958(8)
1.976, 1.917,
1.912(3)
1.975, 1.912,
1.912(3)
1.977, 1.905,
1.919(3)
1.985, 1.917,
1.905(3)
1.922, 1.911,
1.979(6)
1.911, 1.924,
1.989(6)
1.905, 1.916,
1.962(7)
1.917, 1.904,
1.957(8)
1.976, 1.920,
1.902(3)
M(1)–H(2,3)
M(2)–H(1,2)
M(3)–H(2,3)
1.87, 1.80(4)
1.81, 1.73(4)
1.88, 1.81(4)
1.79, 1.79(5)
1.74, 1.72(5)
1.84, 1.82(5)
1.67, 1.68(ꢀ)
1.69, 1.68(ꢀ)
1.68, 1.68(ꢀ)
1.78, 1.78(4)
1.91, 1.92(4)
1.75, 1.68(3)
Bond angles (ꢁ)
M(1)–C(1)–C(2)
M(2)–C(1)–C(2)
M(3)–C(1)–C(2)
126.5(2)
127.5(2)
130.5(2)
126.9(1)
128.4(2)
128.9(2)
129.2(2)
127.1(2)
127.8(2)
126.0(3)
124.0(4)
134.2(3)
128.6(3)
126.1(3)
129.7(3)
128.0(3)
126.6(4)
129.9(4)
125.5(5)
135.6(5)
122.6(5)
127.5(2)
129.2(2)
127.5(2)
C(1)–C(2)–C(3)
C(2)–C(3)–C(4)
177.0(3)
172.8(3)
178.1(2)
176.9(2)
177.2(3)
178.6(3)
174.2(4)
177.5(5)
179.5(5)
176.3(5)
177.7(5)
176.1(5)
178.3(6)
177.5(6)
177.0(6)
176.3(6)
174.1(7)
174.5(8)
176.6(8)
174.3(8)
178.5(2)
179.8(2)
C(3)–C(4)–C(5)
C(n ꢀ 1)–C(n)–C(n01)
178.5(3)
176.7(3) [Si]
˚
For 7: C(5)–C(6) 1.365(9), C(6)–C(7) 1.213(9) A; C(4)–C(5)–C(6) 173.2(8), C(5)–C(6)–C(7) 175.0(8)ꢁ. Values for Fe–C(cp) [range, av., Fe–C(n01)]: for 4: 2.039–2.062(3), 2.046(9), 2.040(3); for 5:
2.052–2.062(6), 2.055(6), 2.063(5); for 6-Ru: 2.035–2.051(5), 2.044(5); for 6-Os: 2.036-2.044(6), 2.041(3), 2.044(6); for 7: 2.032–2.049(7), 2.042(6), 2.038(7) A.
˚

M.I. Bruce et al. / Inorganica Chimica Acta 358 (2005) 1453–1468
1463
Table 2
Bond parameters for 11, 12-Ru, 12-Os and 12-Ru/P
11
12-Ru (2 mol)
12-Os (2 mol)
12-Ru/P
˚
Bond distances (A)
Ru(1)–Ru(2)
Ru(1)–Ru(3)
Ru(2)–Ru(3)
Co(4)–Co(5)
Co(4)–Co(6)
Co(5)–Co(6)
Co(4)–P(4)
Co(5)–P(5)
Ru(1)–C(1)
Ru(2)–C(1)
Ru(3)–C(1)
Co(4)–C(n) [n]
Co(5)–C(n)
Co(6)–C(n)
P(4)–C(0)
2.8523(3)
2.8410(3)
2.8456(3)
2.4893(5)
2.4703(5)
2.4718(4)
2.1987(6)
2.1832(6)
2.088(2)
2.091(2)
2.100(2)
1.906(2) [4]
1.908(2)
1.956(2)
1.839(2)
1.832(2)
1.398(3)
1.232(3)
1.381(3)
2.843(3), 2.841(4)
2.856(3), 2.831(3)
2.843(3), 2.840(4)
2.474(5), 2.464(5)
2.462(4), 2.469(4)
2.463(5), 2.466(5)
2.203(6), 2.190(5)
2.192(6), 2.202(6)
2.11(3), 2.10(3)
2.08(3), 2.10(2)
2.04(2), 2.09(2)
1.87(2), 1.87(2) [6]
1.92(2), 1.91(2)
1.94(2), 1.95(2)
1.80(2), 1.82(2)
1.83(2), 1.81(2)
1.46(3), 1.39(3)
1.19(3), 1.19(3)
1.39(3), 1.36(3)
1.15(3), 1.16(3)
1.44(3), 1.46(3)
2.886(1), 2.883(2)
2.889(1), 2.882(1)
2.880(1), 2.875(2)
2.478(5), 2.479(4)
2.476(4), 2.476(4)
2.473(4), 2.487(4)
2.192(5), 2.199(5)
2.184(6), 2.185(5)
2.13(3), 2.14(2)
2.16(2), 2.15(2)
2.08(2), 2.12(2)
1.88(2), 1.86(2) [6]
1.93(3), 1.93(2)
1.95(2), 1.93(2)
1.82(3), 1.86(2)
1.82(3), 1.82(2)
1.44(3), 1.35(3)
1.14(3), 1.21(3)
1.40(3), 1.39(3)
1.17(2), 1.19(2)
1.41(3), 1.44(2)
2.8378(9)
2.8504(8)
2.8531(10)
2.475(1)
2.480(1)
2.473(1)
2.186(2)
2.196(2)
2.098(6)
2.095(7)
2.095(6)
1.915(7) [6]
1.923(6)
1.939(7)
1.831(6)
1.811(7)
1.388(6)
1.210(6)
1.376(6)
1.204(6)
1.380(6)
P(5)–C(0)
C(1)–C(2)
C(2)–C(3)
C(3)–C(4)
C(4)–C(5)
C(5)–C(6)
Ru(1)–CO(1n)
Ru(2)–CO(2n)
Ru(3)–CO(3n)
Co(4)–CO(4n)
Co(5)–CO(5n)
Co(6)–CO(6n)
1.984, 1.904, 1.895(3)
1.986, 1.920, 1.907(3)
1.972, 1.910, 1.912(3)
1.792, 1.772(3)
1.86, 1.89, 1.93, 2.00, 1.81, 1.93(3)
1.91, 1.88, 1.87, 1.95, 1.98, 1.89(3)
1.97, 1.92, 1.80, 1.99, 1.89, 1.96(3)
1.74, 1.75(3); 1.75, 1.76(3)
1.95, 2.00, 1.83, 1.92, 1.94, 1.91(3)
1.94, 1.97, 1.85, 1.98, 1.89, 1.85(3)
1.94, 1.95, 1.89, 1.90, 1.87, 1.94(2)
1.72, 1.77; 1.76, 1.78(2)
1.845, 1.876(8)
1.971, 1.919, 1.877(8)
1.977, 1.894, 1.905(8)
1.782, 1.782(7)
1.803, 1.790(3)
1.821, 1.788, 1.795(3)
1.83, 1.74(3); 1.82, 1.80(3)
1.88, 1.82, 1.80; 1.84, 1.82, 1.83(3)
1.82, 1.80; 1.81, 1.81(2)
1.96, 1.83, 1.77; 1.75, 1.79, 1.81(3)
1.795, 1.785(8)
1.821, 1.785, 1.811(8)
Bond angles (ꢁ)
Co(4)–P(4)–C(0)
Co(5)–P(5)–C(0)
P(4)–C(10)–P(5)
Ru(1)–C(1)–C(2)
Ru(2)–C(1)–C(2)
Ru(3)–C(1)–C(2)
Co(4)–C(n)–C(n ꢀ 1)
Co(5)–C(n)–C(n ꢀ 1)
Co(6)–C(n)–C(n ꢀ 1)
C(1)–C(2)–C(3)
108.97(8)
110.61(7)
108.9(1)
132.7(2)
124.8(2)
127.0(2)
135.3(2)
135.9(2)
123.2(2)
173.4(2)
172.7(2)
109.3(7), 110.4(6)
110.3(7), 112.3(7)
112.0(9), 109.6(8)
120(2), 125(2)
130(2), 127(2)
132(2), 133(2)
137(2), 138(2)
129(2), 129(2)
129(2), 128(2)
174(3), 170(3)
168(3), 176(3)
180(2), 177(2)
177(3), 177(2)
109.4(8), 109.6(7)
110.8(8), 112.3(7)
111(1), 110.4(9)
124(2), 125(2)
127(2), 128(2)
133(2), 134(2)
138(2), 139(2)
130(2), 126(2)
127(2), 128(1)
172(2), 171(2)
175(3), 177(3)
174(2), 176(3)
177(2), 177(2)
108.9(5)
129.8(7)
129.7(7)
125.5(7)
132.8(8)
136.6(8)
126.3(8)
176.7(9)
179.2(9)
179.0(9)
178.1(9)
C(2)–C(3)–C(4)
C(3)–C(4)–C(5)
C(4)–C(5)–C(6)
˚
For 11: Ru(1)–H(2, 3) 1.78, 1.68(4), Ru(2)–H(1, 3) 1.60, 1.88(4), Ru(3)–H(1, 2) 1.85, 1.85(4). For 12-Ru/P: Ru(1)–P(1) 2.395(2) A.
from which crystals of Ru3(l-H)3(l3-CC„CC„CSi-
Me3)(CO)9 (3) (25 mg, 88%) were obtained (CH2Cl2/
MeOH). Anal. Calc. for (C17H12O9Ru3Si): C, 29.53; H,
1.75. Found: C, 29.41; H, 1.60%. M, 693. IR (CH2Cl2):
out in thf (8 ml) in the presence of Pd(PPh3)4 (4 mg,
0.003 mmol) and CuI (1 mg, 0.005 mmol) at r.t. for 2 h.
Preparative t.l.c. (hexane–acetone 4/1) gave an orange
fraction
CC„CFc)(CO)9 (4) (34 mg, 66%), obtained as orange
crystals (CH2Cl2/MeOH). Anal. Calc. for
(Rf
0.92)
containing
Ru3(l-H)3(l3-
m(C„C) 2110w; m(CO) 2087vs, 2039s, 2029 (sh) cmꢀ1
.
1H NMR: d ꢀ17.87 (s, 3H, RuH), 0.24 (s, 9H, SiMe3).
13C NMR: d 0.1 (SiMe3), 89.3, 94.4, 96.6, 148.9 (C5
chain), 188.0, 189.4 (2 · s, CO). ES-MS (negative ion,
MeOH + NaOMe, m/z): 692, [M ꢀ H]ꢀ; 724,
[M + OMe]ꢀ; 756, [M + OMe + MeOH]ꢀ.
(C22H12FeO9Ru3): C, 33.90; H, 1.55. Found: C, 33.92;
H, 1.48%. M, 781. IR (CH2Cl2): m(C„C) 2108w; m(CO)
2083vs, 2059w, 2034s, 2025 (sh), 1990 (sh) cmꢀ1 1H
.
NMR: d ꢀ17.55 (s, 3H, RuH), 4.20, 4.40 (2 · m, 2 ·
2H, C5H4), 4.21 (s, 5H, Cp). 13C NMR: d 67.9 (Fc Cipso),
68.6, 70.9 (Fc C5H4), 69.6 (Fc Cp), 92.4, 106.2, 158.6 (C3
chain), 189.2, 189.8 (2 · m, CO). ES-MS (positive ion,
MeOH, m/z): 781, M+; (negative ion): 781, Mꢀ.
5.4.5. With Au(C„CFc)(PPh3)
The reaction between 1-Ru (43 mg, 0.066 mmol) and
Au(C„CFc)(PPh3) (44 mg, 0.066 mmol) was carried

1464
M.I. Bruce et al. / Inorganica Chimica Acta 358 (2005) 1453–1468
5.4.6. With Fc0{C„C[Au{P(tol)3}]}2
0.0038 mmol) and CuI (1.5 mg, 0.0008 mmol) were dis-
solved in thf (10 ml) and stirred at r.t. for 3 h. Solvent
was evaporated under vacuum, the residue extracted
with CH2Cl2 and separated by preparative t.l.c. (hex-
ane–acetone, 7/3). A bright yellow band (Rf 0.65) con-
tained {Ru3(l-H)3(CO)9}2{l3:l3-C(C„C)2C} (9) (12.2
mg, 27%) as orange crystals (from CH2Cl2/MeOH).
Anal. Calc. for (C24H6O18Ru6): C 24.25; H, 0.51.
Found: C, 24.30; H, 0.45%. M, 1190. IR (CH2Cl2):
m(C„C) 2128vw, 2106w; m(CO) 2088vs, 2038m, 2030
Similarly, 1-Ru (41 mg, 0.063 mmol) and
Fc0{C„C[Au{P(tol)3}]}2(39 mg, 0.032 mmol) in thf
(10 ml) and CH2Cl2 (5 ml) in the presence of Pd(PPh3)4
(4 mg, 0.003 mmol) and CuI (1 mg, 0.005 mmol) at r.t.
for
H)3(CO)9}2 (5) (10 mg, 23%), obtained as orange crys-
tals (CH2Cl2/MeOH). Anal. Calc. for
2
h
afforded orange Fc0{(l3-C„CC)Ru3(l-
(C34H14FeO18Ru6): C, 29.75; H, 1.03. Found: C,
29.69; H, 1.09%. M, 1374. IR (CH2Cl2): m(C„C)
2109w; m(CO) 2083vs, 2033s, 2024 (sh) cmꢀ1
.
1H
(sh) cmꢀ1. H NMR: d ꢀ17.66 (s, Ru–H). ES-MS (neg-
1
NMR: d ꢀ17.61 (s, 6H, RuH), 4.30, 4.41 (2 · m,
2 · 4H, 2 · C5H4). ES-MS (negative ion, MeOH +
NaOMe, m/z): 1437, [M + OMe + MeOH]ꢀ; 1405,
[M + OMe]ꢀ; 1374, Mꢀ; 660, [Ru3H3(C3C5H4)(CO)9]ꢀ.
ative ion, MeOH, m/z): 1189, [M ꢀ H]ꢀ; (negative ion,
MeOH + NaOMe, m/z): 1221 [M + OMe]ꢀ. This com-
plex is not stable for long in solutions and partly decom-
poses on SiO2.
A mixture of some other thin bands (59.5 mg) was
not investigated.
5.4.7. With Au(C„CC„CFc)(PPh3)
A
mixture of 1-Ru (63 mg, 0.097 mmol),
Au(C„CC„CFc)(PPh3) (67 mg, 0.097 mmol),
Pd(PPh3)4 (6 mg, 0.005 mmol) and CuI (1 mg, 0.005
mmol) in thf (12 ml) was stirred for 1.75 h and then evap-
orated to dryness. Preparative t.l.c. of a dichloromethane
extract of the residue (hexane–acetone 7/3) separated one
major band (Rf 0.72) which contained Ru3(l-H)3{l3-
C(C„C)2Fc}(CO)9 (6-Ru) (40 mg, 52%), obtained as
red-orange needles (CH2Cl2/MeOH). Anal. Calc. for
(C24H12FeO9Ru3): C, 35.88; H, 1.51. Found: C, 35.91;
H, 1.47%. M, 805. IR (CH2Cl2): m(C„C) 2112w; m(CO)
5.4.10. With {Au[P(tol)3]}2{l-(C„C)3}
A solution containing 1-Ru (118.8 mg, 0.2 mmol),
{Au[P(tol)3]}2{l-(C„C)3} (100mg, 0.09 mmol),
Pd(PPh3)4 (5.7 mg, 0.005 mmol) and CuI (1 mg, 0.005
mmol) in thf (12 ml) was stirred at r.t. for 1 h. Solvent
was evaporated under vacuum, the residue dissolved in
CH2Cl2 and separated by preparative t.l.c. (CH2Cl2-
hexane, 1/3). The major bright yellow band (Rf 0.68)
contained 55.9 mg (49%) of {Ru3(l-H)3(CO)9}2{l3:l3-
C(C„C)3C} (10-Ru) which formed small red crystals
(from CH2Cl2). Anal. Calc. for (C26H6O18Ru6): C,
25.75; H, 0.50. Found: C, 25.73; H, 0.52%. M, 1214.
IR (CH2Cl2): m(C„C) 2133w (br); m(CO) 2107w,
1
2086vs, 2037m, 2028 (sh) cmꢀ1. H NMR: d ꢀ17.78 (s,
3H, RuH), 4.25, 4.50 (2 · m, 2 · 2H, C5H4), 4.28 (s,
5H, Cp). 13C NMR: d 65.1 (Fc, Cipso), 69.1 (Fc, C5H5),
70.1, 71.8 (Fc, C5H4), 71.6, 77.8, 86.5, 99.1 (4 · s, C5
chain), 188.2, 189.5 (2 · m, CO). ES-MS (positive ion,
MeOH, m/z): 828, [M + Na]+; (negative ion, MeOH +
NaOMe, m/z): 868, [M + OMe + MeOH]ꢀ; 836,
[M + OMe]ꢀ; 805, Mꢀ; 776, [M ꢀ H ꢀ CO]ꢀ.
m(CO) 2087s, 2038vs, 2028m, 1995w cmꢀ1. H NMR: d
1
ꢀ17.85 (s, RuH). ES-MS (positive ion, MeOH +
NaOMe, m/z): 1237 [M + Na]+; (negative ion,
MeOH + NaOMe, m/z): 1245, [M + OMe]ꢀ; 1213,
[M ꢀ H]ꢀ.
The complex has a very low solubility in all common
organic solvents and decomposes upon standing in solu-
tions and partly on SiO2. The reaction itself is accompa-
nied by some decomposition (formation of black
precipitate).
5.4.8. With Ru{C„CC„CAu[P(tol)3]}(PPh3)2Cp
A solution of Ru{C„CC„CAu[P(tol)3]}(PPh3)2Cp
(50 mg, 0.040 mmol), 1-Ru (26 mg, 0.040 mmol),
Pd(PPh3)4 (5 mg, 0.004 mmol) and CuI (1 mg) in thf
(10 ml) was stirred for 10 min. The product was purified
by preparative t.l.c. (hexane–acetone 7/3, Rf 0.69) to af-
ford Ru3(l-H)3{l3-CC„CC„C[Ru(PPh3)2Cp]}(CO)9
(8) (50 mg, 95%). Anal. Calc. for (C55H38O9P2Ru4): C,
50.46; H, 2.93. Found: C, 50.36; H, 2.82%. IR (CH2Cl2):
5.4.11. With Co3{l3-CC„C[Au(PPh3)]}(l-dppm)
(CO)7
Pd(PPh3)4 (2 mg, 0.002 mmol) and CuI (1.0 mg, 0.005
mmol) were added to a solution containing 1-Ru (24 mg,
0.037 mmol) and Co3{l3-CC„C[Au(PPh3)]}(l-
dppm)(CO)7 (46 mg, 0.037 mmol) in thf (10 ml). After
stirring at r.t. for 3 h and evaporation to dryness (rotary
evaporator), preparative t.l.c. (hexane–acetone 7/3) of
the residue separated three bands. The first (Rf 0.62)
contained brown-black {(OC)9(l-H)3Ru3}CC„CC-
{Co3(l-dppm)(CO)7} (11) (28 mg, 56%; crystals from
CH2Cl2/MeOH). Anal. Calc. for (C45H25Co3O16P2Ru3):
C, 39.64; H, 1.85. Found: C, 39.54; H, 1.75%. M, 1365.
IR (CH2Cl2): m(C„C) 2108w; m(CO) 2083vs, 2054s,
1
m(CO) 2078vs, 2029s cmꢀ1. H NMR: d ꢀ17.44 (s, 3H,
RuH), 4.35 (s, 5H, Cp), 7.07–7.44 (m, 30H, Ph). 13C
NMR (C6D6): d 86.0 (s, Cp), 127.5–134.3 (m, Ph),
190.0, 190.8 (2 · s, CO). 31P NMR: d 49.0 (s, PPh3).
ES-MS (negative ion, MeOH + NaOMe, m/z): 1341,
[M + OMe]ꢀ; (positive ion, MeOH, m/z): 1310, M+.
5.4.9. With {Au[P(tol)3]}2{l-(C„C)2}
1-Ru (50 mg, 0.075 mmol), {Au[P(tol)3]}2{l-
(C„C)2} (32.5 mg, 0.038 mmol), Pd(PPh3)4 (4.5 mg,

M.I. Bruce et al. / Inorganica Chimica Acta 358 (2005) 1453–1468
1465
2037s, 2028 (sh), 2002s, 1991 (sh), 1966w cmꢀ1
.
1H
mg, 4%), identified by comparison with an authentic
sample.
NMR: d ꢀ17.53 (s, 3H, RuH), 3.63, 4.17 (2 · m,
2 · 1H, CH2), 7.05-7.52 (m, 20H, Ph). 13C NMR: d
40.1 (m, CH2), 128.1–132.3 (m, Ph), 188.9, 189.9
(2 · s, Ru–CO), 203.2 (m, Co–CO). 31P NMR: d 33.65
(s, dppm). ES-MS (negative ion, MeOH + NaOMe,
m/z): 1396, [M + OMe]ꢀ. The second band (Rf 0.55)
contained black-brown {(Ph3P)(OC)8(l-H)3Ru3}CC„
CC{Co3(l-dppm)(CO)7} (11-P) (9 mg, 15%; crystals
from CH2Cl2/MeOH). Anal. Calc. for (C62H40Co3O15-
P3Ru3): C, 46.60; H, 2.52. Found: C, 46.64; H, 2.51%.
M, 1599. IR (CH2Cl2): m(C„C) 2096w; m(CO) 2077s,
2053vs, 2037s, 2027m, 2000vs, 1989 (sh), 1974w,
5.5. Reactions of Os3(l-H)3(l3-CBr)(CO)9 (1-Os)
5.5.1. With Au(C„CC„CFc)(PPh3)
The reaction between Os3(l-H)3(l3-CBr)(CO)9 (1-Os)
(51 mg, 0.056 mmol) and Au(C„CC„CFc)(PPh3) (40
mg, 0.058 mmol) was carried out in thf (10 ml) in the
presence of Pd(PPh3)4 (4 mg, 0.003 mmol) and CuI (1
mg, 0.005 mmol) at r.t. for 1 h. Preparative t.l.c. (hex-
ane–acetone 7/3) gave an orange fraction (Rf 0.71) con-
taining Os3(l-H)3(l3- CC„CC„CFc)(CO)9 (6-Os) (48
mg, 80%), obtained as red-orange needles (CH2Cl2/
MeOH). Anal. Calc. for (C24H12FeO9Os3): C, 26.92;
H, 1.13. Found: C, 26.95; H, 1.12%. M, 1072. IR
(CH2Cl2): m(C„C) 2108w; m(CO) 2086vs, 2079 (sh),
1
1963w cmꢀ1. H NMR: d ꢀ17.40 [dt, J (HH) 3.0, J
(HP) 1.2, 1H, RuH], ꢀ 16.84 [dd, J (HH) 3.0, J (HP)
9.0, 2H, RuH], 3.60, 4.26 (2 · m, 2 · 1H, CH2), 7.06–
7.53 (m, 35H, Ph). 31P NMR: d 27.66 (s, PPh3), 33.88
[s(br), dppm]. ES-MS (negative ion, MeOH + NaOMe,
m/z): 1630, [M + OMe]ꢀ. The third band (Rf 0.47) con-
tained recovered Co3{l3-CC„C[Au(PPh3)]}(l-dppm)
(CO)7 (9.2 mg, 20%).
1
2028 (sh), 2023vs, 2013w, 1982w (br) cmꢀ1. H NMR:
d ꢀ19.03 (s, 3H, OsH), 4.22, 4.49 (2 · m, 2 · 2H,
C5H4), 4.28 (s, 5H, Cp). 13C NMR: d 65.2 (Fc Cipso),
68.9, 71.8 (Fc C5H4), 70.0 (Fc Cp), 69.6, 71.9, 81.0,
99.0, 103.1 (5 · s, C5 chain), 164.8, 166.6 (2 · s, Os–
CO). ES-MS (negative ion, MeOH + NaOMe, m/z):
1135, [M + OMe + MeOH]ꢀ; 1103, [M + OMe]ꢀ; 1071,
[M ꢀ H]ꢀ; 1043–959, [M ꢀ H ꢀ nCO]ꢀ (n = 1–4).
5.4.12. With Co3{l3-CC„CC„C[Au(PPh3)]}
(l-dppm)(CO)7
Similarly, the product from 1-Ru (35 mg, 0.054
mmol) and Co3{l3-CC„CC„C[Au(PPh3)]}(l-dppm)-
(CO)7 (69 mg, 0.054 mmol) in thf (10 ml) containing
Pd(PPh3)4 (4 mg, 0.003 mmol) and CuI (1 mg, 0.005
mmol) at r.t. for 2.5 h was separated into three frac-
tions. Band 1 (Rf 0.56) contained {(OC)9(l-H)3Ru3}C-
(C„C)2C{Co3(l-dppm)(CO)7} (12-Ru) (52 mg, 69%;
crystals from CH2Cl2/MeOH). Anal. Calc. for
(C47H25Co3O16P2Ru3): C, 40.68; H, 1.82. Found: C,
40.51; H, 1.61%. M, 1389. IR (CH2Cl2): m(C„C)
2110w; m(CO) 2086vs, 2058s, 2037m, 2021 (sh), 2010s,
5.5.2. With Au{(C„C)3Fc}(PPh3)
Similarly, 1-Os (23 mg, 0.026 mmol) and
Au{(C„C)3Fc}(PPh3) (19 mg, 0.027 mmol) reacted in
the presence of Pd(PPh3)4 (2 mg, 0.002 mmol) and CuI
(1 mg, 0.005 mmol) in thf (10 ml) for 1.5 h at r.t. After
preparative t.l.c. (hexane–acetone 3/1), an orange band
(Rf 0.73) gave red-orange crystals of Os3(l-H)3(l3-
C(C„C)3Fc}(CO)9 (7) (9.2 mg, 32%). Anal. Calc. for
(C26H12FeO9Os3): C, 28.52; H, 1.10. Found: C, 28.60;
H, 1.07%. M, 1096. IR (CH2Cl2): m(C„C) 2112w;
m(CO) 2088vs, 2080 (sh), 2028 (sh), 2031 (sh), 2025vs,
1987 (sh), 1979 (sh), 1965 (sh) cmꢀ1 1H NMR: d
.
ꢀ17.60 (s, 3H, RuH), 3.50, 4.45 (2 · m, 2 · 1H, CH2),
7.22-7.54 (m, 20H, Ph). 13C NMR: d 42.9 (m, CH2),
79.2, 97.6, 109.4, 116.7 (4 · s, C6 chain), 128.4-134.9
(m, Ph), 188.4, 189.6 (2 · s, Ru–CO), 202.0 (m, Co–
CO). 31P NMR: d 34.73 (s, dppm). ES-MS (negative
ion, MeOH + NaOMe, m/z): 1420, [M + OMe]ꢀ; 1389,
Mꢀ. Brown-black crystals of {(Ph3P)(OC)8(l-H)3Ru3}-
C(C„C)2C{Co3(l-dppm)(CO)7} (12-Ru/P) (20 mg,
23%; crystals from CH2Cl2/MeOH) were obtained from
the second band (Rf 0.51). Anal. Calc. for
(C64H40Co3O15P3Ru3): C, 47.39; H, 2.49. Found: C,
47.31; H, 2.52%. M, 1623. IR (CH2Cl2): m(C„C)
2098w; m(CO) 2079ms, 2056vs, 2036m, 2025 (sh),
1
2016w, 1982w (br) cmꢀ1. H NMR: d ꢀ19.09 (s, 3H,
OsH), 4.24 (m, 7H, 2H of C5H4 + Cp), 4.52 (m, 2H,
C5H4). 13C NMR: d 69.5, 72.4 (Fc C5H4), 70.3, (Fc
Cp), 63.3, 65.6, 66.8, 69.1, 71.9, 78.8, 102.0, 102.3 (C7
chain + Fc Cipso), 164.4, 166.5 (2 · m, Os–CO). ES-MS
(negative
ion,
MeOH + NaOMe,
m/z):
1127,
[M + OMe]ꢀ.
5.5.3. With {Au[P(tol)3]}2C6
To a mixture of 1-Os (27.7 mg, 0.030 mmol) and
{Au[P(tol)3]}2C6 (16 mg, 0.015 mmol) in thf (7 ml)
was added Pd(PPh3)4 (6 mg, 0.005 mmol) and CuI (2
mg, 0.01 mmol). After stirring for 30 min at r.t., pre-
parative t.l.c. (hexane–acetone 2/1) separated an yellow
fraction (Rf 0.56) which afforded orange crystals of
{Os3(l-H)3(CO)9}2{l3:l3-C(C„C)3C} (10-Os) (6.7 mg,
26%). Anal. Calc. for (C26H6O18Os6): C, 17.87; H,
0.35. Found: C, 17.78; H, 0.00%. M, 1748. IR (CH2Cl2):
1
2009vs, 1977w cmꢀ1. H NMR: d ꢀ17.43 [dt, J (HH)
3.0, J (HP) 1.2, 1H, RuH], ꢀ 16.85 [dd, J (HH) 3.0, J
(HP) 9.6, 2H, RuH], 3.45, 4.46 (2 · m, 2 · 1H, CH2),
7.16–7.45 (m, 35H, Ph). 31P NMR: d 28.26 (s, PPh3),
34.62 (br s, dppm). ES-MS (negative ion, MeOH +
NaOMe, m/z): 1654, [M + OMe]ꢀ. Band 3 (Rf 0.46) con-
tained {Co3(l-dppm)(CO)7}2{l3:l3-C(C„C)4C} (3.7
1
m(C„C) 2108w; m(CO) 2089vs, 2026vs cmꢀ1. H NMR:

Table 3
Crystal data and refinement details
Compound
2
3
4
5
6-Ru
6-Os
Formula
MW
C18H8O9Ru3
671.46
C17H12O9Ru3Si
691.57
C22H12FeO9Ru3
779.39
C34H14FeO18Ru6
1372.74
triclinic
C24H12FeO9Ru3
803.42
triclinic
C24H12FeO9Os3
1070.8
triclinic
Crystal system
Space group
monoclinic
P21/c
monoclinic
P21/n
monoclinic
P21/n
ꢀ
ꢀ
ꢀ
P1
P1
P1
˚
a (A)
9.1897(6)
9.9975(6)
23.437(2)
10.5050(8)
9.3637(7)
24.173(2)
9.3272(7)
10.2497(7)
26.465(2)
8.0630(6)
11.4130(9)
12.502(1)
100.702(2)
105.044(2)
104.162(2)
1038
9.343(1)
10.131(1)
14.749(2)
109.054(3)
93.606(3)
97.397(3)
1300
9.3462(5)
10.0654(5)
14.7074(7)
108.618(6)
93.386(1)
97.362(1)
1293
˚
b (A)
˚
c (A)
a (ꢁ)
b (ꢁ)
c (ꢁ)
94.553(2)
90.660(2)
96.335(2)
3
˚
V (A )
2146
2378
2515
Z
4
2.078
2.13
4
1.932
1.97
4
2.058
2.38
1
2.195
2.53
2
2.052
3.8
2
2.750
15.3
Dcalc (g cmꢀ3
)
l (mmꢀ1
)
Crystal size (mm)
Tmin/max
0.13 · 0.12 · 0.07
0.89
75
0.23 · 0.12 · 0.07
0.79
75
0.22 · 0.13 · 0.11
0.76
70
0.16 · 0.10 · 0.05
0.77
75
0.54 · 0.32 · 0.03
0.75
67
0.28 · 0.10 · 0.06
0.41
75
2hmax (ꢁ)
Ntot
44121
49140
45641
20724
17633
25997
N (Rint
No
)
11255 (0.031)
8921
0.035
12503 (0.038)
10086
0.032
11037 (0.027)
9461
0.029
10572 (0.038)
7292
0.042
9273 (0.040)
6669
0.045
13318 (0.046)
9857
0.041
R
Rw(nw)
0.042 (0.5)
0.047 (8)
0.052 (1.5)
0.061 (0.7)
0.064 (4)
0.045 (0.5)
Compound
7
9
11
12-Ru
12-Os
12-Ru/P
Formula
MW
C
26H12FeO9Os3
C24H6O18Ru6
1188.71
monoclinic
P21/c
C45H25Co3O16P2Ru3.CH2Cl2
C47H25Co3O16P2Ru3
1387.66
monoclinic
Pn
C47H25Co3O16Os3P2
1655.05
monoclinic
Pn
C64H40Co3O15P3Ru3 ÆCH2Cl2
1694.83
monoclinic
P21/c
1448.57
monoclinic
P21/c
1706.88
monoclinic
P21/c
Crystal system
Space group
˚
a (A)
16.224(1)
14.015(1)
12.198(1)
103.558(2)
2096
8.2622(7)
12.941(1)
16.900(1)
101.392(2)
1771
18.906(1)
11.5463(7)
23.900(2)
98.192(2)
5164
12.160(2)
37.529(6)
13.226(2)
112.752(2)
5566
12.186(2)
37.527(5)
13.258(2)
112.774(2)
5590
24.815(5)
12.219(2)
22.902(4)
106.058(3)
6673
˚
b (A)
˚
c (A)
b (ꢁ)
3
˚
V (A )
Z
4
2.697
14.7
4
2.228
2.56
4
1.863
2.21
4
1.656
1.79
4
1.966
7.8
4
1.699
1.61
Dcalc (g cmꢀ3
)
l (mmꢀ1
)
Crystal size (mm)
Tmin/max
0.42 · 0.12 · 0.04
0.40
69
0.34 · 0.31 · 0.28
0.79
75
0.39 · 0.31 · 0.18
0.78
75
0.42 · 0.31 · 0.30
0.81
50
0.29 · 0.17 · 0.14
0.59
58
0.33 · 0.17 · 0.07
0.76
50
2hmax (ꢁ)
Ntot
53761
23733
107312
27093 (0.038)
20107
37162
51024
43792
N (Rint
No
)
11524 (0.065)
9375
0.037
9205 (0.025)
6792
0.030
9156 (0.040)
8855
0.086
25949 (0.038)
23838
0.056
12368 (0.050)
9706
0.056
R
0.041
0.052 (0.9)
Rw(nw)
0.081 (1)
0.032 (2)
0.129 (4.5)
0.091(9)
0.092 (5)

M.I. Bruce et al. / Inorganica Chimica Acta 358 (2005) 1453–1468
1467
d ꢀ19.05 (s, 3H, OsH). ES-MS (negative ion, MeOH +
NaOMe, m/z): 1779, [M + OMe]ꢀ. Only limited spectro-
scopic data were obtained because of the low solubility
of this complex.
which were eventually modelled using isotropic forms
for C, O. In processing the data merged normally; xabs
for the two structures were 0.17(4), 0.05(1). Large differ-
˚
ence map residues were observed ca. 1 A from the metal
atom in each case (4, 6 e Aꢀ3, respectively). The cause of
˚
5.5.4. With Co3{l3-C(C„C)2Au(PPh3)}
(l-dppm)(CO)7
these anomalous behaviours is not clear-cut (pseudo-
symmetry, co-crystallisation or disorder?) and derivative
results should be treated with due caution. Core hydro-
gen atoms were not located.
12-Ru/P. The solvent and one nearby phenyl ring (11)
were modelled as disordered over pairs of sites, occu-
pancies set at 0.5 after trial refinement.
Pd(PPh3)4 (2 mg, 0.002 mmol) and CuI (1 mg, 0.005
mmol) were added to a mixture of 1-Os (27 mg, 0.029
mmol) and Co3{l3-C(C„C)2Au(PPh3)}(l-dppm)(CO)7
(38 mg, 0.030 mmol) in thf (12 ml). After stirring at r.t.
for 1 h and removal of solvent, preparative t.l.c. (hex-
ane–acetone 7/3) of the residue gave one major band (Rf
0.62) which afforded {(OC)9(l-H)3Os3}C(C„C)2C
{Co3(l-dppm)(CO)7} (12-Os) (38 mg, 79%; brown-black
crystals from CH2Cl2/MeOH). Anal. Calc. for
(C47H25Co3O16Os3P2): C, 34.11; H, 1.52. Found: C,
34.06; H, 1.40%. M, 1656. IR (CH2Cl2): m(C„C)
2112w; m(CO) 2086vs, 2056s, 2024s, 2008s, 1968 (sh)
6. Supplementary material
Full details of the structure determination (except
structure factors) have been deposited with the Cam-
bridge Crystallographic Data Centre as CCDC
237538-237547 (complexes 2–5, 6-Os, 7, 9, 11, 12-Ru,
12-Ru/P, respectively), 244531 (6-Ru) and 245225 (12-
Os). Copies of this information may be obtained free
of charge from The Director, CCDC, 12 Union Road,
Cambridge CB2 1EZ, UK (Fax: +44 1223 336 033;
e-mail: deposit@ccdc.cam.ac.uk or www.ccdc.cam.
ac.uk).
cmꢀ1
.
1H NMR: d ꢀ18.82 (s, 3H, OsH), 3.45, 4.43
(2 · m, 2 · 1H, CH2), 7.19–7.51 (m, 20H, Ph). 13C
NMR: d 42.8 (m, CH2), 71.5, 98.9, 103.9, 121.1 (4 · s,
C6 chain), 128.1–135.0 (m, Ph), 165.0, 166.6 (2 · s, Os–
CO), 202.1 (m, Co–CO). ES-MS (negative ion, MeOH +
NaOMe, m/z): 1687, [M + OMe]ꢀ; 1655, [M ꢀ H]ꢀ.
5.6. Structure determinations
Full spheres of diffraction data to the indicated limits
were measured at ca. 153 K using a Bruker AXS CCD
area-detector instrument. Ntot reflections were merged
to N unique (Rint quoted) after ‘‘empirical’’/multiscan
absorption correction (proprietary software), No with
F > 4r(F) being used in the full matrix least squares refine-
ment. All data were measured using monochromatic Mo
Acknowledgements
We thank the Australian Research Council for sup-
port. We are grateful to Professor B.K. Nicholson (Uni-
versity of Waikato, Hamilton, New Zealand), for
obtaining the mass spectra for us. Johnson Matthey
plc, Reading, UK, is thanked for a generous loan of
RuCl3.nH2O.
˚
Ka radiation, k = 0.71073 A. Anisotropic thermal param-
eter forms were refined for the non-hydrogen atoms,
(x, y, z, Uiso H being constrained at estimated values.
)
Conventional residuals R, Rw on |F| are given [weights:
(r2(F) + 0.00nwF2)ꢀ1]. Neutral atom complex scattering
factors were used; computation used the XTAL 3.7 pro-
gram system [34]. Pertinent results are given in the figure
(which shows non-hydrogen atoms with 50% probability
amplitude displacement envelopes and hydrogen atoms
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