Heterometallic complexes containing 1,1′-(C{triple bond, long}C)2Fc′ units linking two different metal centres

Article abstract of DOI:10.1016/j.jorganchem.2006.11.035

Proto-desilylation of 1-(Me₃SiC{triple bond, long}C)-1′-{Cp^*(dppe)RuC{triple bond, long}C}Fc′ (1) afforded the corresponding ethynyl derivative 2, from which the green Co₂(μ-dppm)_n(CO)_8-2n (n = 0, 1) adducts 3 and 4 were obtained. Replacement of the ethynyl proton in reactions between 2 and AuCl(PPh₃), Hg(OAc)₂ or FeCl(dppe)Cp^* gave complexes 1-(RC{triple bond, long}C)-1′-{Cp^*(dppe)RuC{triple bond, long}C}Fc′ [R = Au(PPh₃) 5, 1/2Hg 6, Fe(dppe)Cp^* 8]; the latter gave bis-vinylidene 9 with MeI, characterised (as was 2) by a single crystal X-ray study. Oxidative coupling of 2 (CuCl/tmeda/acetone, air) gave diyne 10, while coupling of 5 with Co₃(μ₃-CBr)(μ-dppm)(CO)₇ afforded 1-{Cp^*(dppe)RuC{triple bond, long}C}-1′-{(OC)₇(μ-dppm)Co₃(μ₃-CC{triple bond, long}C)}Fc′ (11). Cyclic voltammetric measurements indicated that there was no significant electronic coupling between the end-groups through the ferrocene centre in any of these compounds.

Full text of DOI:10.1016/j.jorganchem.2006.11.035

Journal of Organometallic Chemistry 692 (2007) 1748–1756
www.elsevier.com/locate/jorganchem
Heterometallic complexes containing 1,10-(C„C)2Fc0 units linking
two different metal centres
a,
a
a
a
Michael I. Bruce *, Paul A. Humphrey , Martyn Jevric , Gary J. Perkins ,
b
b
Brian W. Skelton , Allan H. White
a
School of Chemistry and Physics, University of Adelaide, Adelaide, South Australia 5005, Australia
Chemistry M313, SBBCS, University of Western Australia, Crawley, Western Australia 6009, Australia
b
Received 18 October 2006; received in revised form 23 November 2006; accepted 23 November 2006
Available online 1 December 2006
Abstract
Proto-desilylation of 1-(Me3SiC„C)-10-{Cp*(dppe)RuC„C}Fc0 (1) afforded the corresponding ethynyl derivative 2, from which the
green Co2(l-dppm)n(CO)8ꢀ2n (n = 0, 1) adducts 3 and 4 were obtained. Replacement of the ethynyl proton in reactions between 2 and
AuCl(PPh3), Hg(OAc)2 or FeCl(dppe)Cp* gave complexes 1-(RC„C)-10-{Cp*(dppe)RuC„C}Fc0 [R = Au(PPh3) 5, 1/2Hg 6, Fe(dp-
pe)Cp* 8]; the latter gave bis-vinylidene 9 with MeI, characterised (as was 2) by a single crystal X-ray study. Oxidative coupling of 02
(CuCl/tmeda/acetone, air) gave diyne 10, while coupling of 5 with Co3(l3-CBr)(l-dppm)(CO)7 afforded 1-{Cp*(dppe)RuC„C}-1 -
{(OC)7(l-dppm)Co3(l3-CC„C)}Fc0 (11). Cyclic voltammetric measurements indicated that there was no significant electronic coupling
between the end-groups through the ferrocene centre in any of these compounds.
ꢀ 2006 Elsevier B.V. All rights reserved.
Keywords: Carbon-tricobalt cluster; Carbon chains; Electronic communication; Ferrocene; Gold(I) phosphine complexes; Ethynyl complexes; Ruthen-
ium-phosphine
1. Introduction
of these derivatives, including isolation of the stable 17-e
cation in [Fe(C„CFc)(PPh3)2Cp]PF6 [2b], unusual involve-
ment of the alkynyl goup in formation of fulvalenyl-ruthe-
nium derivatives occurs [3]. A further subset of related
compounds contains two FcC„C groups attached to a sin-
gle metal centre, such as Ru(C„CFc)2(dppx)2 (x = m, e)
[4,5]. However, there are few examples of complexes derived
from 1,10-bis(ethynyl)ferrocene, Fc0(C„CH)2, and related
compounds [6–8].
Recently, we have reported several complexes containing
Ru(PP)Cp0 groups end-capping the 1,10-Fc0(C„C–)2
nucleus [9]. Similar ruthenocene complexes, and compounds
of the type Ru{(C„C)nFc}(PP)Cp0 [PP = (PPh3)2, dppm,
dppe, dppf; Cp0 = Cp, Cp*] (n = 1,2,3) have also been
made [10]. In the course of our studies on the ferrocene com-
plexes, we discovered a route to the monometal0lated
derivative 1-(Me3SiC„C)-10-{Cp*(dppe)RuC„C}Fc (1),
which we have subsequently used to make a series of asym-
metric 1,10-bis(alkynyl)ferrocenes containing at least two
There is continuing interest in complexes containing
ethynylferrocene moieties attached to transition metal cen-
tres as a result of the well-known redox properties associated
with the ferrocenyl (Fc) centre. Of the thirty crystallograph-
ically characterised compounds containing r-bonded
FcC„C– ligands [1], several contain a second redox-active
metal group, and it has been of interest to examine the
degree of electronic communication between the two
metal-containing groups. A series of papers by Sato and
coworkers [2,3] have described the properties of ethynylfer-
rocene complexes containing M(PP)Cp0 fragments
[M = Fe, Ru; PP = (PPh3)2, dppe, dmpe; Cp0 = Cp, Cp*;
not all combinations]. In addition to the ready oxidation
*
Corresponding author. Tel./fax: +61 8 8303 4358.
E-mail address: michael.bruce@adelaide.edu.au (M.I. Bruce).
0022-328X/$ - see front matter ꢀ 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2006.11.035

M.I. Bruce et al. / Journal of Organometallic Chemistry 692 (2007) 1748–1756
1749
redox-active centres. This allowed a study of the interactions
of two or more metal centres through the ferrocene group.
These syntheses and preliminary electrochemical studies of
the resulting complexes are reported herein.
The Ru(dppe)Cp* fragment is similar to many others
which have been reported, with Ru–P distances ranging
between 2.2625 and 2.2673(8) and Ru–C(cp*) between
˚
2.213 and 2.275(3) A, with angles about the ruthenium con-
sistent with pseudo-octahedral coordination [P(1)–Ru–P(2)
84.77, 83.46(3); P(1,2)–Ru–C(1) range 83.07–85.52(8)ꢁ].
The separations Ru–C(1), C(1)–C(2), C(2)–C(201),
C(2040)–C(2060) and C(2060)–C(2070) [2.012(3), 1.220(5),
2. Results and discussion
˚
Precursor 1 (Scheme 1) was prepared in 46% yield as
described earlier [9], from 1,10-(Me3SiC„C)2Fc0 and one
equivalent of RuCl(dppe)Cp* in the presence of KF. Treat-
ment of 1 with [NBu4]F in thf containing a small amount of
water resulted in ready proto-desilylation and formation of
orange 1-(HC„C)-10-{Cp*(dppe)RuC„C}Fc0 (2). Char-
acterisation was by elemental microanalysis (as with all
complexes described subsequently) and spectroscopy. The
IR spectrum contained m(„CH) at 3305 and 3281 cmꢀ1
along with m(C„C) at 2109 and 2073 cmꢀ1, while the acet-
ylenic proton appears as a singlet at d 2.54 in the 1H NMR
spectrum. Other resonances are characteristic of the Fc0
and Ru(dppe)Cp* groups. Further discussion of the
NMR spectra is given below.
The molecular structure of 2 has been determined by a
single-crystal X-ray diffraction study. The unit cell contains
two independent molecules, which differ in the disposition
of the C5H4C„CH group around the Fe-C5 axis with
respect to the Cp*(dppe)RuC„CC5H4 group (Fig. 1,
Table 1).
1.433(5), 1.429(5), 1.188(5) A, respectively; values for mol-
ecule 1 given] confirm the presence of the alkynyl groups,
with the C„CH triple bond being significantly shorter
than the ruthenium-bonded group, as a result of back-
bonding from the metal into the latter. The values may
be compared with those determined earlier for
Ru(C„CFc)(dppe)Cp* which has Ru–P 2.2482(7),
˚
2.2746(7), Ru–C(1) 2.013(2) and C(1)–C(2) 1.206(4) A.
The ferrocene-1,10-diyl moiety has no anomalous structural
features, the two independent molecules differing by the
torsion angles between the two C„C bonds about the
Fe–C(0) axis, which are ꢀ159.9 and 64.3ꢁ. The two alkynyl
groups approach linearity, with angles at C(1), C(2),
C(12060) and C(22060) being 177.3(3), 174.9(3), 177.1(4)
and 177.6(4)ꢁ, respectively.
Further derivatisation of 2 has been carried out and
these reactions are summarised in Schemes 1 and 2. As
expected, 2 reacts with Co2(l-dppm)n(CO)8ꢀ2n (n = 0, 1)
to give the corresponding adducts 3 (as a non-crystallisable
green oil) and 4, respectively, in which the dicobalt
Ru
C
C
Ph2P
PPh2
Fe
C
C H
Ru
C
C
Co2(μ-dppm)n(CO)8-2n
Ph2P
(OC)nCo
Co(CO))n
PPh2
Fe
P
P
(1)
C
C
SiMe3
(3) n = 3, PP = -
(4) n = 2, PP = dppm
Ru
C
C
TBAF
Ph2P
PPh2
Fe
(2)
C
CH
AuCl(PPh3)
/NaOMe
Co3(μ-CBr)(μ-dppm)(CO)7
Ru
C
C
Ru
C
C
Ph2P
Ph2P
Ph2P
Co
PPh2
PPh2
Fe
Fe
PPh2
Co(CO)2
C
C Au(PPh3)
C
C C
(11)
(5)
Co
(CO)3
Scheme 1.

1750
M.I. Bruce et al. / Journal of Organometallic Chemistry 692 (2007) 1748–1756
Table 1
˚
Selected bond distances (A) and angles (ꢁ)
Complex
2a
9b
1122
1112
˚
Bond distances (A)
Ru–P(1)
Ru–P(2)
1121
2.2673(8), 2.2653(8)
2.2625(7), 2.2666(7)
2.240–2.268(3),
2.279(1)
2.250(1)
2.187–2.255(5)
1111
1021
102
Ru–C(cp)
P(11)
1202
1201
2.217–2.275(3)
1203
1204
1011
(Av.)
2.255(6), 2.25(2)
2.012(3), 2.022(3)
1.220(5), 1.212(4)
2.22(3)
1.799(5)
1.329(7)
1.502(8)
110
101
1031
Ru–C(1)
C(1)–C(2)
C(2)–C(3)
C(2)–C(201)
Fe–C(cp)
103
Fe(1)
1205
11
12
Ru(1)
120
105
1.433(5), 1.438(5)
2.027–2.067(3),
2.036–2.076(3)
2.052(15), 2.046(6)
1.429(5),
1.428(5) [C(2020)]
1.188(5), 1.183(6)
1.479(7)
1201’
1207’
104
P(12)
1212
1204’
1041
2.036–2.076(3),
2.040–2.056(3)
2.046(15)
1206’
1051
1221
1205’
1211
(Av.)
C(2040)–C(2060)
1222
C(2060)–C(2070)
Bond angles (ꢁ)
P(1)–Ru–P(2)
P(1)–Ru–C(1)
P(2)–Ru–C(1)
Ru–C(1)–C(2)
C(1)–C(2)–C(3)
C(1)–C(2)–C(201)
C(3)–C(2)–C(201)
C(2040)–C(2060)–C(2070)
84.77(3), 83.46(3)
83.07(9), 83.57(9)
85.14(8), 85.52(8)
177.3(3), 177.6(3)
83.43(4)
94.9(2)
82.3(2)
178.3(4)
119.6(5)
125.4(4)
114.8(4)
2122
2021
174.9(3), 178.5(3)
2121
2112
177.1(4),
177.6(4) [C(2020)]
2207’
2206’
2011
P(21)
a
2111
Values for two independent molecules given.
For Ru, read M (disordered Fe, Ru).
2202
b
202
203
201
2203
2204
2201
21
22
2031
nances at d 43.4 and 82.3 (ratio 1/2) were assigned to the
PPh3 and dppe ligands, respectively. Of interest are the
metal-bonded C(sp) atoms, which resonate at d 102.07
(„CAu) and 119.45 („CRu) as a doublet [J(CP) =
28.3 Hz] and triplet [J(CP) = 25.5 Hz], respectively; only
one of the other C(sp) atoms is found, at d 104.36.
2051
Ru(2)
204
Fe(2)
2205
220
205
P(22)
2212
2204’
2221
2041
2211
2205’
2222
The mercury(II) derivative Hg{1-C„C-10-[C„CRu-
(dppe)Cp*]Fc0}2 (6) was obtained from a reaction carried
out between 2 and Hg(OAc)2 in refluxing thf overnight.
The IR spectrum of 6 contained four m(C„C) bands
between 2145 and 2075 cmꢀ1, while the NMR spectra con-
tained resonances anticipated from the component groups.
In particular, proton resonances at d 1.65 and 13C signals at
d 10.79 and 92.93 confirmed the presence of the Cp*
groups, and resonances at dC 103.84, 106.08, 119.60 and
122.02 [triplet, J(CP) = 24.1 Hz] were assigned to carbons
of the C„C triple bonds, the latter to the „CRu atoms.
Previously we have described the synthesis, characterisa-
tion and elec0trochemical behaviour of the symmetrical
derivative, 1,1 -{Cp*(dppe)RuC„C}2Fc0 (7) [7]. The avail-
ability of 2 enabled us to prepare the related asymmetric
complex 1-{Cp*(dppe)FeC„C}-10-{Cp*(dppe)RuC„C}
Fc0 (8), which was obtained from 2 and FeCl(dppe)Cp*
in the presence of Na[BPh4]. This complex contained
strong m(C„C) bands at 2100, 2074 and 2057 cmꢀ1 (cf.
2107, 2082 cmꢀ1 for the Ru2 analogue [9]) and resonances
Fig. 1. Plots of the two molecules of 1-(HC„C)-10-{Cp*(dppe)RuC
„C}Fc0 (2), showing the differing dispositions of the –C„CH substituents.
carbonyl fragment is attached to the less hindered of the
two C„C triple bonds. This is shown most clearly in the
13C NMR spectra, in which the chemical shifts of the car-
bons of the C„CH fragment show a down-field shift [from
d 74.0 and 84.2 to 75.3 and 83.9 (for 3), 76.9 and 89.7 (for
4)], while the resonances for the C„C–Ru group remain
close to the values found for 2. Other data are also consis-
tent with this structural interpretation, detailed assign-
ments being given in Section 4.
Treatment of 2 with AuCl(PPh3) in the presence of
NaOH in methanol resulted in the formation of 1-
{(Ph3P)AuC„C}-10-{Cp*(dppe)RuC„C}Fc0 (5) as a light
orange solid. The IR spectrum of 5 contained two m(C„C)
bands at 2105 and 2077 cmꢀ1, while the NMR spectra con-
tained the resonances anticipated from the three major
fragments present. In the 31P NMR spectrum, two reso-
1
in the H NMR spectrum at d 1.56 and 1.69, assigned by
comparison with 7 to the Fe- and Ru-bonded Cp* Me

M.I. Bruce et al. / Journal of Organometallic Chemistry 692 (2007) 1748–1756
1751
FeCl(dppe)Cp*
Ru
C
C
Ru
C
C
Ph2P
Ph2P
Na[BPh4]
PPh2
Fe
Ph2P
Fe
PPh2
Fe
PPh2
C
C
(2)
C
CH
(8)
X = - : Cu2+/tmeda/O2
X = Hg: Hg(OAc)2
MeI / NH4[PF6]
2+
Ru
Ph2P
C
C
PPh2
Ru
C
C
Ph2P
Fe
Me
Ph2P
PPh2
Fe
PPh2
Fe
C
C
C
C
X
C
C
Me
(9)
Fe
Ph2P
Ru
(6) X = Hg
(10) X = -
Ph2P
C
C
Scheme 2.
groups, respectively. The 31P NMR spectrum contained
resonances at d 82.11 and 101.45, similarly assigned to
the Ru- and Fe-bonded dppe ligands. The solubility of this
complex was not high enough for a 13C NMR spectrum to
be measured.
The structure of the cation of 9 found in the single-crys-
tal X-ray determination of the tetraphenylborate salt is
shown in Fig. 2. Selected bond distances and angles are
listed in Table 1.
The centrosymmetric cation is isostructural with the
Ru2 analogue and the iron and ruthenium atoms are fully
scrambled, as is now customary with complexes of
this type, particularly [{Cp*(dppe)Fe}CC-CC{Ru(dp-
pe)Cp*}]n+ (n = 0, 1, 2) [5]. The structure itself offers no
surprises, confirming the formulation proposed on the
basis of the chemistry and spectroscopy. Only average
However, treatment of 8 with MeI in the presence of
Na[BPh4] afforded the bis-vinylidene [1-{Cp*(dppe)-
Fe@C@CMe}-10-{Cp*(dppe)Ru@C@CMe}Fc0](BPh4)2 (9)
1
as red-brown crystals. The H NMR spectrum contained
Cp* Me signals at d 1.40 and 1.57 together with the vinyl-
idene Me groups at d 1.16 and 1.45. The Cp* Me and ring
carbons are found at d 10.19 and 10.25 (FeCp*), and 99.43
and 102.52 (RuCp*), with the @CMe groups resonating at
d 9.79 and 12.67. The Fe@C and Ru@C signals are down-
field at d 349.13 and 359.53, showing triplet J(CP) cou-
plings of 17.4 and 33.4 Hz, respectively. In the 31P NMR
spectrum, the dppe ligands give signals at d 75.8 (Ru)
and 90.1 (Fe). The ES mass spectrum contains a strong
M2+ ion at m/z 743.
˚
˚
M–P [2.250, 2.279(1) A] and M–C distances [1.799(5) A]
can be measured, but these approximate to the average
of similar distances found in related complexes, such as
the diruthenium analogue [Ru–P 2.298(1), 2.298(1), Ru–
˚
C
1.859(4) A [9]] and [Fe(@C@CHPh)(dppe)Cp*]PF6
[Fe–P, 2.222(2), 2.219(2), Fe–C 1.763(7) [11]. Geometries
around the metal atoms are pseudo-octahedral, with
P(1)–M–P(2) 83.43(4) and P(1,2)–M–C(1) 82.3, 94.9(2)ꢁ.
1021
102
1031
101
105
1011
1051
103
Ru,Fe(1)
P(1)
111
212
1
202
2
112
Fe(2)
203
204
211
3
221
222
205
10
20
Fig. 2. Plot of the cation in [1-{Cp*(dppe)Fe@C@CMe}-10-{Cp*(dppe)Ru@C@CMe}Fc0](BPh4)2 (9).

1752
M.I. Bruce et al. / Journal of Organometallic Chemistry 692 (2007) 1748–1756
˚
The C(1)–C(2) separation of 1.329(7) A indicates a bond
in 11)]. In the cation of 8, the resonances are shifted to
lower field, at d 75.8 (Ru-dppe) and 90.1 (Fe-dppe).
Electrochemistry. One of the reasons for preparing this
set of compounds was to measure the extent of any elec-
tronic interaction between the two metal centres bridged
by the ferrocene-1,10-diethynyl moiety. In previous studies,
we and others have concluded that, while there is extensive
delocalisation (strong interaction) in oxidised complexes
derived from M(C„CFc)(dppe)Cp0 (M = Fe, Ru;
PP = (PPh3)2, dppe; Cp0 = Cp, Cp*], the ferrocene group
acts as an insulator when inserted into the C4 chain of com-
plexes {Ru(PP)Cp0}2(l-C„CC„C) [9].
˚
order approaching 2, while C(2)–C(3) [1.502(8) A] and
C(2)–C(201) [1.479(7) A] are in accord with the expected
˚
C(sp2)–C(sp3) and C(sp2)–C(sp2) separations. The angle
at atom C(1) [178.3(4)ꢁ] confirms its sp hybridisation,
while the three angles at C(2) [range 114.8–125.4(4)ꢁ] are
consistent with the expected sp2 hybridisation of this
atom. With a centre of symmetry in the molecule, the
two substituents necessarily have a torsion angle of 180ꢁ
about the C(0)–Fe–C(00) axis.
Oxidative dimerisation of 8 under Hay conditions
(CuCl/tmeda/acetone/ai0r) afforded the expected diyne 1-
{Cp*(dppe)RuC„C}Fc -10,100-C„CC„C- Fc0{C„CRu-
(dppe)Cp*}-1000 (10) as an orange solid in 78% yield. The
The electrochemical responses of each complex
described herein were examined by cyclic voltammetry
(Table 2). All potentials were referenced against an internal
ferrocene standard and converted to the saturated calomel
m(C„C) bands were at 2144m, 2108 w and 2072s cmꢀ1
,
while the Cp* Me resonance is at d 1.66. In the 13C
NMR spectrum, the Cp* Me and ring carbons resonate
at d 10.78 and 92.91, respectively, with the „C atoms at
d 72.88, 80.97, 103.60 and 122.70t [J(CP) 24.1 Hz], the lat-
ter being assigned to the „CRu atoms. The molecular ion
is found in the ES MS at m/z 1734.
electrode (SCE) scale. With scan rates v P 100 mV sꢀ1
,
waves representing one-electron redox processes were
found. For 1, 2, 5 and 6, two potentials, separated by
600–670 mV, can be assigned to oxidations at the ruthe-
nium and ferrocene centres, respectively. The shift from
corresponding values for model compounds Ru(C„CPh)-
(dppe)Cp* (+0.245 V) and FcC„CH reflect the interac-
tions between both redox centres through the C2 link. In
the case of 5, a third process, at +1.25 V, may be associated
with the gold centre.
Coordination of the dicobalt carbonyl fragments to one
of the C„C triple bonds results in little change in these
potentials for 3, but three waves, at ꢀ0.02, +0.58 and
+0.87 V, are found for 4, indicating that considerable elec-
tronic interaction occurs between the three metal centres.
Also found are reduction waves at ꢀ1.40 and ꢀ1.57 V
for 3 and 4, respectively, which are associated with pro-
cesses taking place at the dicobalt centres.
We were able to utilise the phosphine-gold halide elim-
ination reaction [6] to prepare a complex in which the fer-
rocene-1,10-bis(ethynediyl) nucleus bridges mononuclear
ruthenium and carbon-tricobalt cluster centres. Treatment
of the gold derivative 5 with Co3(l3-CBr)(l-dppm)(CO)7
in a Pd(0)/Cu(I)-catalysed reaction gave 1-{Cp*(dppe)-
RuC„C}-10-{(l-dppm)(OC)7Co3(l3-CC„C)}Fc0 (11) as
a dark red powder in 60% yield. The IR spectrum con-
tains a weak m(C„C) band at 2114 cmꢀ1 and terminal
m(CO) bands between 2068 and 1966 cmꢀ1. The 1H
NMR spectrum contained a signal for the Cp* Me groups
at d 1.70, while resonances for the Cp* Me and ring car-
bons are at d 10.78 and 92.94 in the 13C NMR spectrum.
Other signals assigned to the „C atoms occur at d
103.84, 108.74 and 114.46. Both NMR spectra contain
resonances for the dppm and dppe ligands in the usual
regions, while signals at d 34.3 and 82.1 in the 31P
NMR spectrum arise from the dppm and dppe ligands,
respectively. In the ES MS, the peak at m/z 1636 is
assigned to M+.
The trinuclear complex 8 shows three processes, at
ꢀ0.29, +0.17 and +0.71 V, potentials which lie between
Table 2
Electrochemistry of some disubstituted ferrocene complexes
Complexa
E1/V
E2/V
DE/mV
E3/V
1
+0.09
+0.09
+0.11
ꢀ0.02
+0.04
+0.10
ꢀ0.29
ꢀ0.31
+0.04
+0.44
+0.44
+0.11
+0.75
+0.76
+0.72
+0.58
+0.69
+0.72
+0.17
ꢀ0.13
+0.68
+0.87d
+0.89d
+0.77
660
670
610
600
650
620
NMR spectra. The 13C NMR spectra of these complexes
contain resonances characteristic of the ligands present,
minor variations being ascribed to the different metal cen-
tres. Thus, the Ru(dppe)Cp* group gives rise to resonances
at d 10.7–10.8 and 92.8–93.0 (Cp* Me and ring carbons),
29.5–31.0 (dppe CH2), and 128.0–140.8 (Ph), while the
Fc0 resonances are found as four signals for the two differ-
ent C5H4 groups (d 69.4–70.1, 70.2–72.0, 71.6–72.5 and
73.2–74.0; exceptions to the latter are found with 3 and
4, where the lowest field resonances are at d 72.5 and
71.8, respectively) and the two ipso carbons (d 64.3–69.7
and 78.2–79.4, the latter assigned to the ring bearing the
Ru group because of its constancy). The 31P NMR spectra
contain resonances for the Ru-dppe ligand (d 82.1–82.4)
and for other phosphine ligands if present [d 41.0 (dppm
in 4), 43.4 (PPh3 in 5), 101.5 (Fe-dppe in 8), 34.3 (dppm
2
3b
4c
+0.87
+1.25d
5
6
8
+0.71
+0.64
+1.29
80 [Fe2]
80 [Ru2]
9
90 [Ru2]
10
+0.97
Measured as 1 mM solutions in CH2Cl2 containing 0.5 M [NBu4]BF4 at
100 mV sꢀ1, referenced to internal FeCp2/[FeCp2]+ = 0.46 V.
a
For 8 and 9, primed complexes are the symmetrical Fe2 and Ru2
complexes.
b
Reduction process at ꢀ1.40 V (irrev.).
c
Reduction process at ꢀ1.57 V (irrev.).
d
Irreversible.

M.I. Bruce et al. / Journal of Organometallic Chemistry 692 (2007) 1748–1756
1753
those found for the corresponding di-iron (ꢀ0.31, ꢀ0.13,
+0.64 V) and diruthenium complexes (+0.04, +0.68,
+1.29 V), suggesting that all three compounds have very
similar interactions between the metal centres, again
through the C2 links. The related bis(methylvinylidene)
complex shows two waves, at +0.44 and +0.89 V.
were dissolved in CDCl3 contained in 5 mm sample tubes.
Chemical shifts are given in ppm relative to internal tetra-
1
methylsilane for H and 13C NMR spectra and external
H3PO4 for 31P NMR spectra. Electrospray mass spectra
(ES MS) were obtained from samples dissolved in MeOH
unless otherwise indicated. Solutions were injected into a
Varian Platform II spectrometer via a 10 ml injection loop.
Nitrogen was used as the drying and nebulising gas. Chem-
ical aids to ionisation were used [13].
Electrochemical samples (1 mM) were dissolved in
CH2Cl2 containing 0.5 M [NBu4]BF4 as the supporting
electrolyte. Cyclic voltammograms were recorded using a
PAR model 263 apparatus, with a saturated calomel elec-
trode, with ferrocene as internal calibrant (FeCp2/
[FeCp2]+ = +0.46 V). The cell contained a Pt-mesh work-
ing electrode, Pt wire counter and pseudo-reference elec-
trodes. Elemental analyses were by CMAS, Belmont,
Vic., Australia.
Diyne 10 gives three waves at +0.11, +0.77 and
+0.97 V, suggesting that the extended unsaturated
system linking the two ruthenium centres similarly allows
a degree of communication between them. Of interest in
this connection are the redox properties of Os3(l3 - g2-
FcC2C„CFc)(l-CO)(CO)9
and
Os3(l3 - g4-FcC4Fc)
(CO)11 [12]. In the former, there are two closely spaced oxi-
dation waves (DEp = 57 mV) for the non-equivalent Fc
groups. The latter complex gives two resolved 1-e processes
separated by DEp = 184 mV, suggesting that there is signif-
icant electronic communication between the two formally
equivalent Fc groups here.
3. Conclusions
4.3. Reagents
The serendipitous discovery of a route to the asymmet-
ric dialkynylferrocene 1-(Me3SiC„C)-10-{Cp*(dppe)RuC
„C}Fc0 1 has allowed the subsequent preparation of sev-
eral related compounds, including the protodesilylated
complex 2, and others in which the acetylenic hydrogen
in 2 has been replaced by Au(PPh3) 5, Hg/2 6 or Fe(dp-
pe)Cp* 7, while the (l3-C)Co3(l-dppm)(CO)7 derivative
11 was obtained from 5 and Co3(l3-CBr)(l-dppm)(CO)7.
In addition, complexes containing Co2(l-dppm)n(CO)6ꢀ2n
(n = 0, 1) groups attached to one of the C„C triple0bonds
of 2, and the novel diyne 1-{Cp*(dppe)0R00 uC„C}Fc -10,100-
C„CC„C- Fc0{C„CRu(dppe)Cp*}-1 10 have also been
prepared and characterised. Some electrochemical studies
of these complexes are also reported.
1-(Me3SiC„C)-10-{Cp*(dppe)RuC„C}Fc0 (1) was
obtained as previously described [9].
4.4. Preparation of 1-(HC„C)-10-{Cp*(dppe)RuC„C}Fc0
(2)
TBAF (1.0 M solution in thf, 3 ml, 3.0 mmol) was added
to a solution of 1-(Me3SiC„C)-10-{Cp*(dppe)RuC„C}
Fc0 (1) (1700 mg, 1.81 mmol) in thf (100 ml) and the mix-
ture was stirred for 16 h at r.t. After removal of solvent
in vacuum, a diethyl ether extract of the residue was filtered
through a pad of neutral alumina. Evaporation of the fil-
trate afforded pure 1-(HC„C)-10-{Cp*(dppe)RuC„C}Fc0
(2) as an orange solid (1320 mg, 84%). Anal. Found: C,
69.32; H, 5.59. Calcd (C50H48FeP2Ru): C, 69.20; H, 5.58;
M, 868. IR (nujol, cmꢀ1): 3305 m, 3281 m [m(„CH)],
4. Experimental
1
2109w, 2073s [m(C„C)], 1585w 1571w. H NMR (C6D6):
4.1. General
d 1.63 (s, 15 H, C5Me5), 1.90-2.05, 2.70-2.90 (2 · m,
2 · 2 H, CH2), 2.54 (s, 1H, „CH), 3.90-3.92, 4.03-4.05,
4.17-4.19, 4.30-4.32 (4 · m, 4 · 2H, C5H4), 7.07-7.32,
7.90-7.96 (2 · m, 16H + 4H, Ph). 13C NMR (C6D6): d
10.75 (C5Me5), 29.78-30.69 (m, CH2), 64.49 (Fc ipso),
69.39 (C5H4), 71.11 (C5H4), 72.02 (C5H4), 73.53 (C5H4),
74.01 (C„C), 79.05 (Fc ipso), 84.19 (C„C), 92.94
(C5Me5), 103.68 (Cb), 122.09 [t, J(CP) 25.6 Hz, Ru-C„],
128.67-140.44 (m, Ph). 31P NMR (C6D6): d 82.1 (dppe).
ES MS (MeOH, positive ion, m/z): 868, M+.
All reactions were carried out under dry nitrogen,
although normally no special precautions to exclude air
were taken during subsequent work-up. Common solvents
were dried, distilled under argon and degassed before use.
Separations were carried out by preparative thin-layer
chromatography on glass plates (20 · 20 cm2) coated with
silica gel (Merck, 0.5 mm thick).
4.2. Instruments
4.5. Reactions of 1-(HC„C)-10-{Cp*(dppe)RuC„C}Fc0
(2)
IR 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.
Nujol mull spectra were obtained from samples mounted
between NaCl discs. NMR spectra were recorded on a Var-
ian 2000 instrument (1H at 300.13 MHz, 13C at 75.47 MHz,
31P at 121.503 MHz). Unless otherwise stated, samples
(a) With Co2(CO)8. Solid Co2(CO)8 (100 mg,
0.292 mmol) was added to a solution of 1-(HC„C)-10-
{Cp*(dppe)RuC„C}Fc0 (2) (53 mg, 0.061 mmol) in dry
thf (10 ml) and the mixture was stirred at r.t. for 16 h.
Chromatography on basic alumina (acetone/hexane 1/9)

1754
M.I. Bruce et al. / Journal of Organometallic Chemistry 692 (2007) 1748–1756
afforded adduct 1-{l-HC2[Co2(CO)6]}-10- {Cp*(dppe)RuC
„C}Fc0 (3) as a green oil (68 mg, 97%). Anal. Found: C,
58.37; H, 4.15. Calcd (C56H48Co2FeO6P2Ru): C, 58.30;
H, 4.19; M, 1154. IR (cyclohexane, cmꢀ1): m(CO) 2087 m,
119.45 [t, J(CP) 25.5 Hz, Ru-C„], 127.79–140.77 (m,
Ph). 31P NMR (C6D6): d 43.4 (PPh3), 82.3 (dppe). ES
MS (MeOH, positive ion, m/z): 1326, M+; 1784,
[M + Au(PPh3)]+.
1
2048s, 2023s, 2017s (sh), 2005w. H NMR (C6D6): d 1.63
(d) With Hg(OAc)2. A solution containing 1-(HC„C)-
10-{Cp*(dppe)RuC„C}Fc0 (2) (103 mg, 0.119 mmol) and
Hg(OAc)2 (18 mg, 0.063 mmol) in thf (20 ml) was heated
at reflux point for 16 h. Concentration to ca. 3 ml and addi-
tion to rapidly stirred hexane (100 ml) gave a precipitate,
which after cooling to ꢀ20 ꢁC overnight was filtered off
and washed with hexane to give pure Hg{1-(C„C)-10-
[C„CRu(dppe)Cp*]Fc0}2(6) (69 mg, 60%). Anal. Found:
C, 62.14; H, 4.86. Calcd (C100H94Fe2HgP4Ru2): C, 62.10;
H, 4.90; M, 1934. IR (nujol, cmꢀ1): 2145 m, 2123w,
(s, 15H, C5Me5), 1.95–2.10, 2.70–2.85 (2 · m, 2 · 2H,
CH2), 3.96–3.97, 4.10–4.11, 4.26–4.27 (3m, 2H + 4H +
2H, C5H4), 5.78 (s, 1H, m), 7.07 [s (br), Ph], 7.20–7.37,
7.93–7.99 (2 · m, 10H + 4H, Ph). 13C NMR (C6D6): d
10.72 (C5Me5), 30.03–30.95 (m, CH2), 69.61 (C5H4),
71.96 (C5H4), 72.04 (C5H4), 72.46 (C5H4), 75.33 (C„C),
79.36 (Fc ipso), 83.89 (C„C), 93.03 (C5Me5), 103.71
(Cb), 122.78 [t, J(CP) 25.8 Hz, RuC„], 128.86-140.48 (m,
Ph), 200.74 (CO). 31P NMR (C6D6): d 82.4 (dppe). ES
MS (MeOH, positive ion, m/z): 1154, M+.
1
2111w, 2075s [m(C„C)], 1585w, 1572w. H NMR (C6D6):
(b) With Co2 (l-dppm)(CO)6. A mixture of 1-
d 1.65 (s, 30H, C5Me5), 1.95–2.15, 2.75–2.95 (2 · m,
2 · 4H, CH2 of dppe), 3.98–3.99, 4.10–4.11, 4.24–4.25,
4.33–4.34 (4 · m, 4 · 4H, C5H4), 7.08–7.09, 7.23–7.38,
7.98–8.03 (3 · m, 12H + 20H + 8H, Ph). 13C NMR
(C6D6): d 10.79 (C5Me5), 30.18–30.80 (m, CH2 of dppe),
65.43 (Fc ipso), 65.59 (C5H4), 70.98 (C5H4), 72.47 (C5H4),
73.92 (C5H4), 78.97 (Fc ipso), 92.93 (C5Me5), 103.84 (Cb),
106.08 (C„C), 119.60 (C„C), 122.02 [t, J(CP) 24.1, Ru–
C„], 128.07–140.30 (m, Ph). 31P NMR (C6D6): d 82.1
(dppe). ES MS (MeOH, positive ion, m/z): 1934, M+.
(e) With FeCl(dppe)Cp*. A mixture of 1-(HC„C)-10-
{Cp*(dppe)RuC„C}Fc0 (2) (100 mg, 0.115 mmol), FeCl-
(dppe)Cp* (90 mg, 0.144 mmol) and Na[BPh4] (89 mg,
0.26 mmol) was heated in refluxing MeOH (40 ml) for 1 h.
After cooling to r.t., a small piece of sodium (ca 20 mg)
was added. The mixture was stirred a further 15 min and
the resulting precipitate was collected, washed with MeOH
and hexane, and recrystallised (thf/MeOH) to give pure 1-
(HC„C)-10-{Cp*(dppe)RuC„C}Fc0
(2)
(47 mg,
0.054 mmol) and Co2(l-dppm)(CO)6 (38 mg, 0.57 mmol)
was heated in refluxing thf (20 ml) for 16 h. Purification
by chromatography on basic alumina (acetone/hexane 1/
9)
gave
adduct
1-{l-HC2[Co2(l-dppm)(CO)4]}-10-
{Cp*(dppe)RuC„C}Fc0 (4) as a green solid (61 mg,
76%). Anal. Found: C, 64.02; H, 4.81. Calcd (C79H70Co2-
FeO4P4Ru): C, 64.02; sH, 4.76; M, 1482. IR (cyclohexane,
cmꢀ1): m(CO) 2079w, 2021s, 1994s (sh), 1969s, 1952w. H
1
NMR (C6D6): d 1.68 (s, 15H, C5Me5), 2.88–3.01 (m, 4H,
CH2 of dppe), 3.22–3.27 (m, 2H, CH2 of dppm), 4.16 (m,
2H, C5H4), 4.23 (m, 2H, C5H4), 4.31 (m, 2H, C5H4), 4.57
(m, 2H, C5H4), 6.01 (s, 1H, „CH), 6.89, 7.08, 7.27–7.38,
8.00–8.05 (4 · m, 12H + 6H + 18H + 4H, Ph). 13C NMR
(C6D6): d 10.80 (C5Me5), 29.84–30.56 (m, CH2 of dppe),
40.79 [t, J(CP) 20.0 Hz, CH2 of dppm], 66.25 (Fc ipso),
69.64 (C5H4), 71.48 (C5H4), 71.71 (C5H4), 71.83 (C5H4),
76.88 (C„C), 78.37 (Fc ipso), 89.71 (C„C), 92.88
(C5Me5), 104.44 (Cb), 120.14 [t, J(CP) 25.5 Hz, Ru–C„],
127.90–140.58 (m, Ph), 205.35 (CO), 208.05 (CO). 31P
NMR (C6D6): d 41.0 (dppm), 82.2 (dppe). ES MS (MeOH,
positive ion, m/z): 1482, M+.
{Cp*(dppe)FeC„C}-10-{C„CRu(dppe)
Cp*}Fc0
(8)
(112 mg, 67%). Anal. Found: C, 70.29; H, 6.43. Calcd
(C86H86Fe2P4Ru): C, 70.93; H, 5.95; M, 1456. IR (nujol,
1
cmꢀ1): 2100w, 2074s, 2057s [m(C„C)], 1585w, 1572w. H
NMR (C6D6): d 1.56 (s, 15H, Cp*-Fe), 1.69 (s, 15H, Cp*-
Ru), 1.80–2.05, 2.70–3.00 [2 · m (br), 2 · 4H, CH2 of dppe],
4.03, 4.13, 4.31–4.35 (3 · m, 2 · 2H + 4H, C5H4), 7.06–
7.36, 7.99–8.04, 8.08–8.14 (3 · m, 32H + 4H + 4H, Ph).
31P NMR (C6D6): d 82.1 (dppe-Ru), 101.5 (dppe-Fe). ES
MS (MeOH, positive ion, m/z): 1456, M+.
(c) With AuCl(PPh3). 1-(HC„C)-10-{Cp*(dppe)RuC
„C}Fc0 2 (203 mg, 0.224 mmol) was added to a solution
containing AuCl(PPh3) (113 mg, 0.228 mmol) and NaOH
(393 mg, 9.8 mmol) in MeOH (45 ml) and the mixture
was stirred at r.t. for 16 h. After this time, the product
was filtered off, washed with MeOH and dried to give 1-
{(Ph3P)AuC„C}-10-{Cp*(dppe)RuC„C}Fc0 (5) as a light
orange solid (255 mg, 86%). Anal. Found: C, 61.61; H,
4.76. Calcd (C68H63AuFeP3Ru): C, 61.55; H, 4.79; M,
(f) Reaction of 1-{Cp*(dppe)FeC„C}-10-{C„CRu-
(dppe)Cp*}Fc0 (8) with MeI. MeI (10 drops, excess) was
added to a degassed solution of 1-{Cp*(dppe) FeC„C}-
10-{C„CRu(dppe)Cp*}Fc0 (8) (70 mg, 0.48 mmol) and
Na[BPh4] (52 mg, 0.15 mmol) in thf (10 ml) and the solu-
tion was heated at reflux point for 16 h. After removal of
solvent, cautious addition of hexane to a filtered CH2Cl2
extract of th residue gave a biphasic system from which
bis-vinylidene [1-{Cp*(dppe)Fe@C@CMe}-10-{Cp*(dppe)-
Ru@C@CMe}Fc0](BPh4)2 (9) separated as red-brown crys-
tals. Anal. Found: C, 76.40; H, 6.70. Calcd
(C136H132B2Fe2P4Ru): C, 76.88; H, 6.26; M, 1486. IR
1
1326. IR (nujol, cmꢀ1): m(C„C) 2105w, 2077s. H NMR
(C6D6): d 1.67 (s, 15H, C5Me5), 1.90–2.10, 2.88–3.01
(2 · m, 2 · 2H, CH2 of dppe), 3.97 (m, 2H, C5H4), 4.25
(m, 2H, C5H4), 4.37 (m, 2H, C5H4), 4.51 (m, 2H, C5H4),
6.85–6.95, 7.04–7.06, 7.20–7.30, 7.36–7.41, 8.02–8.07
(5 · m, 10H + 6H + 11H + 4H + 4H, Ph). 13C NMR
(C6D6): d 10.82 (C5Me5), 30.04–30.66 (m, CH2 of dppe),
69.58 (C5H4), 69.72 (Fc ipso), 70.15 (C5H4), 72.31 (C5H4),
73.66 (C5H4), 78.18 (Fc ipso), 92.81 [t, J(CP) 2.3 Hz,
C5Me5], 102.07 [d, J(CP) 28.3 Hz, Au–C„], 104.36 (Cb),
1
(nujol, cmꢀ1): 1632 m, 1579w. H NMR (C6D6): d 1.16
(s, 3H, Me), 1.40 (s, 15H, C5Me5), 1.45 (s, 3H, Me), 1.57

M.I. Bruce et al. / Journal of Organometallic Chemistry 692 (2007) 1748–1756
1755
(s, 15H, Cp*), 2.10–2.40, 2.40–2.70 (2 · m, 2 · 4H, CH2 of
dppe), 3.19, 3.22, 3.70, 3.78 (4 · m, 4 · 2H, C5H4), 6.83–
7.54 (m, 80H, Ph). 13C NMR (C6D6): d 9.79 (Me), 10.19
(C5Me5), 10.25 (C5Me5), 12.67 (Me), 28.06–29.80 (m,
CH2 of dppe), 66.11 (C5H4), 66.41 (C5H4), 67.94 (C5H4),
77.21 (C5H4), 79.95 (Fc ipso), 82.40 (Fc ipso), 99.43
(C5Me5), 102.52 (C5Me5), 116.25 (C„C), 126.90 (C„C),
121.52-165.07 (m, Ph), 349.13 [t, J(CP) 17.4 Hz, Ru@C],
359.53 [t, J(CP) 33.4 Hz, Fe@C]. 31P NMR (C6D6): d
75.8 (dppe-Ru), 90.1 (dppe-Fe). ES MS (MeOH, positive
6.72-7.36, 7.59-7.62, 7.93-7.96 (3 · m, 32H + 4H + 4H,
Ph). 13C NMR (C6D6): d 10.78 (C5Me5), 29.49-30.46
(m, CH2 of dppe), 40.78 (CH2 of dppm), 67.61 (Fc ipso),
70.05 (C5H4), 71.26 (C5H4), 71.61 (C5H4), 73.19 (C5H4),
79.11 (Fc ipso), 92.94 (C5Me5), 103.84 (Cb), 108.74
(C„C), 114.46 (C„C), 128.25-140.12 (m, Ph), 202.80
(CO). 31P NMR (C6D6):
d 34.3 [s (br), dppm],
82.1 (dppe). ES MS (MeOH, positive ion, m/z): 1636,
M+.
ion, m/z): 743, M2+
.
4.8. Structure determinations
4.6. Oxidative dimerisation of 1-(HC„C)-10-
{Cp*(dppe)RuC„C}Fc0 (2)
Full spheres of diffraction data were measured at ca
153 K using a Bruker AXS CCD area-detector instrument.
Ntot reflections were merged to N unique (Rint cited) after
‘‘empirical’’/multiscan absorption correction (proprietary
software), No with F > 4r(F) being used in the full matrix
least squares refinements. All data were measured using
A solution of tmeda (150 mg, 1.29 mmol) and CuCl
(103 mg, 1.04 mmol) in acetone (10 ml) was added to 0a con-
tinuously oxygenated solution of 1-(HC„C)-1 -{Cp*
(dppe)RuC„C}Fc0 (2) (99 mg, 0.114 mmol) in acetone
(20 ml) over a period of 1 h. After removal of solvent,
the residue was purified by chromatography (basic alu-
mina, benzene) 0 to give 1-{Cp*(dppe)RuC„C}Fc0-10,
100-C„CC„C-Fc {C„CRu(dppe)Cp*}-1000 (10) (77 mg,
78%) as an orange solid. Anal. Found: C, 69.14; H, 5.43.
Calcd (C100H94Fe2P4Ru2): C, 69.28; H, 5.47; M, 1734. IR
(nujol, cmꢀ1): 2144m, 2108w, 2072s [m(C„C)], 1585w,
˚
monochromatic Mo Ka radiation, k = 0.71073 A. Aniso-
tropic displacement parameter forms were refined for the
non-hydrogen atoms, (x, y, z, Uiso)H being included, con-
strained at estimates. Conventional residuals R, Rw on F2
are quoted [weights: (r2(F2) + nwF2)ꢀ1]. Neutral atom com-
plex scattering factors were used; computation used the
XTAL 3.7 program system [14].
Pertinent results are given in the Figures (which show
non-hydrogen atoms with 50% probability amplitude dis-
placement ellipsoids and hydrogen atoms with arbitrary
1
1571w. H NMR (C6D6): d 1.66 (s, 30H, C5Me5), 1.95–
2.15, 2.70–2.90 (2 · m, 2 · 4H, CH2 of dppe), 3.94–3.95,
4.04–4.05, 4.19–4.20, 4.27–4.28 (4 · m, 4 · 4H, C5H4),
7.07 [s (br)], 7.25–7.38, 7.94–8.00 (3 · m, 12H + 20H
+ 8H, Ph). 13C NMR (C6D6): d 10.78 (C5Me5), 29.89–
30.56 (m, CH2 of dppe), 64.33 (Fc ipso), 69.35 (C5H4),
71.51 (C5H4), 72.14 (C5H4), 74.01 (C5H4), 72.88 (C„C),
79.31 (Fc ipso), 80.97 (C„C), 92.91 (C5Me5), 103.60
(Cb), 122.70 [t, J(CP) 24.1, Ru–C„], 127.91–140.49 (m,
Ph). 31P NMR (C6D6): d 82.2 (dppe). ES MS (MeOH, posi-
tive ion, m/z): 1734, M+.
˚
radii of 0.1 A) and in Table 1. 0
Compound 2 1-(HC„C)-1 -{Cp*(dppe)RuC„C}Fc0 ”
C50H48FeP2Ru, MW = 867.80. Triclinic, space group P1,
˚
bar, a = 12.9309(8), b = 14.5237(9), c = 22.066(1) A,
3
˚
a = 92.381(2), b = 91.502(2), c = 100.478 (2)ꢁ, V = 4069 A ,
Z = 4, 2hmax = 60ꢁ. Dc = 1.416 g cmꢀ3
,
l = 0.84 mmꢀ1
,
Tmin/max = 0.93. Crystal 0.56 · 0.41 · 0.12 mm. Ntot
=
93722, N = 21058 (Rint = 0.057), No = 15363, R = 0.044,
Rw = 0.094, nw = 18.
Compound
9
[1-{Cp*(dppe)Fe@C@CMe}-10-
{Cp*(dppe)Ru@C@CMe}Fc0](BPh4)2 ” C136H132B2Fe2P4
Ru, MW = 2124.95. Monoclinic, space group P21/n,
4.7. Preparation of 1-{Cp*(dppe)RuC„C}-10-{(l-
dppm)(OC)7Co3 (l3-CC„C)}Fc0 (11)
˚
a = 16.139(2), b = 18.243(3), c = 18.468(3) A, b = 98.921
(3)ꢁ, V = 5371 A , Z = 2. 2hmax = 50ꢁ. Dc = 1.314 g cmꢀ3
,
3
A mixture of 1-{Cp(dppe)RuC„C}-10-{(Ph3P)Au}Fc0
(5) (87 mg, 0.066 mmol), Co3(l3-CBr)(l-dppm)(CO)7
(56 mg, 0.066 mmol), Pd(PPh3)4 (4 mg, 0.003 mmol) and
CuI (1 mg, 0.005 mmol) in thf (15 ml) was stirred at r.t.
for 30 min. After removal of solvent, preparative t.l.c.
of the residue (acetone/hexane 1/2) gave a major red-pur-
ple band (Rf 0.35) from which 1-{Cp*(dppe)RuC„C}-10-
{(l-dppm)-(OC)7Co3(l3-CC„C)}Fc0 (11) (64 mg, 60%)
was obtained as a dark red powder (CH2Cl2/MeOH).
Anal. Found: C, 59.70; H, 3.97. Calcd (C83H69Co3FeO7-
P4Ru): C, 60.93; H, 4.25; M, 1636. IR (nujol, cmꢀ1):
2114vw(br) [m(C„C)], 2068(sh), 2056vs, 2005vs, 1991
(sh), 1966 (sh) [m(CO)]. 1H NMR (C6D6): d 1.70 (s,
15 H, C5Me5), 1.98-2.01, 2.74-2.77 (2 · m, 2 · 4H, CH2
of dppe), 3.07-3.13, 4.42-4.48 (2 · m, 2 · 1H, CH2 of
dppm), 4.23, 4.24, 4.33, 4.58 (4 · m, 4 · 2H, C5H4),
˚
l = 0.52 mmꢀ1
,
Tmin/max = 0.92. Crystal 0.26 · 0.16 ·
0.16 mm. Ntot = 51324, N = 9429 (Rint = 0.088), No =
7098, R = 0.056, Rw = 0.11, nw = 4.5.
Variata. The molecule was modelled as disordered about
a crystallographic inversion centre located at the FcFe
atom, RuFe(1) being modelled as a composite, with no
components of the disorder resolvable further afield.
Acknowledgements
We thank Professor Brian Nicholson (University of
Waikato, Hamilton, New Zealand) for providing the mass
spectra and the ARC for support of this work. We are
grateful for a generous loan of RuCl3 Æ nH2O from Johnson
Matthey plc, Reading.

1756
M.I. Bruce et al. / Journal of Organometallic Chemistry 692 (2007) 1748–1756
[3] (a) M. Sato, Y. Kawata, H. Shintate, Y. Habata, S. Akabori, K.
Unoura, Organometallics 16 (1997) 1693;
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(b) M. Sato, A. Iwai, M. Watanabe, Organometallics 18 (1999)
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[4] x = m: M.C.B. Colbert, J. Lewis, N.J. Long, P.R. Raithby, A.J.P.
White, D.J. Williams, J. Chem. Soc. Dalton Trans. (1997) 99;
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Toupet, P.H. Dixneuf, Inorg. Chim. Acta 272 (1998) 188.
[6] Y. Mori, T. Kashi, T. Kakesada, H. Komatsu, H. Yamazaki, M.
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[7] O. Lavastre, M. Even, P.H. Dixneuf, A. Pacreau, J.P. Vairon,
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CCDC 619080 and 619081 contain the supplementary
crystallographic data for 2 and 9. These data can be
obtained free of charge via http://www.ccdc.cam.ac.uk/
conts/retrieving.html, or from the Cambridge Crystallo-
graphic Data Centre, 12 Union Road, Cambridge CB2
1EZ, UK; fax: (+44) 1223-336-033; or e-mail: depos-
it@ccdc.cam.ac.uk. Supplementary data associated with
this article can be found, in the online version, at
doi:10.1016/j.jorganchem.2006.11.035.
[8] N.J. Long, A.J. Martin, R. Vilar, A.J.P. White, D.J. Williams, M.
Younus, Organometallics 18 (1999) 4261.
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KOR; M = Fe, XAGSUU, ZUJJAP; M = Ru, PIXVOH, PUDNIL,
PUTLOF, REQRIO, ULAGUT, ULAHAQ, ULAHEU; M = Os,
HERXEH; M = Pt: HAJFON, HEHFAB, MIRVIS, RAMKEV,
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