Preparation, structure and some chemistry of FcC{triple bond, long}CC{triple bond, long}CC{triple bond, long}CRu(dppe)Cp

Article abstract of DOI:10.1016/j.jorganchem.2007.02.043

The synthesis of Fc(C{triple bond, long}C)₃Ru(dppe)Cp (2) from Fc(C{triple bond, long}C)₃SiMe₃ and RuCl(dppe)Cp is described, together with its reactions with tcne to give the tetracyano-dienyl FcC{triple bond, long}CC{tri

Full text of DOI:10.1016/j.jorganchem.2007.02.043

Journal of Organometallic Chemistry 692 (2007) 2564–2574
www.elsevier.com/locate/jorganchem
Preparation, structure and some chemistry
of FcC„CC„CC„CRu(dppe)Cp
a,
a
a
Michael I. Bruce *, Paul A. Humphrey , Martyn Jevric ,
b
b
Brian W. Skelton , Allan H. White
a
School of Chemistry and Physics, University of Adelaide, Adelaide, SA 5005, Australia
Chemistry M313, SBBCS, University of Western Australia, Crawley, WA 6009, Australia
b
Received 14 February 2007; accepted 28 February 2007
Available online 12 March 2007
Abstract
The synthesis of Fc(C„C)3Ru(dppe)Cp (2) from Fc(C„C)3SiMe3 and RuCl(dppe)Cp is described, together with its reactions with
tcne to give the tetracyano-dienyl FcC„CC„C{C[@C(CN)2]}2Ru(dppe)Cp (3) and -cyclobutenyl FcC„CC„C{C@CC(CN)2C(CN)2}-
Ru(dppe)Cp (4), with Co2(l-dppm)n(CO)8ꢀ2n (n = 0, 1) to give FcC2{Co2(CO)6}C2{Co2(CO)6}C„CRu(dppe)Cp (5) and FcC„
CC„CC2{Co2(l-dppm)(CO)4}Ru(dppe)Cp (6), respectively, and with Os3(CO)10(NCMe)2 to give Os3{l3-C2C„CC„C[Ru(dppe)Cp]}-
(CO)10 (7). On standing in solution, the latter isomerises to the cyclo-metallated derivative Os3(l-H){l3-C[Ru(dppe)Cp]CCC[(g-
C5H3)FeCp]}(CO)8 (8). X-ray structural determinations of 1, 2, 6 and 7 are reported.
ꢀ 2007 Elsevier B.V. All rights reserved.
Keywords: Ferrocene; Ruthenium; Triyne; Cyanoalkene; Dicobalt; Triosmium cluster; X-ray structures
1. Introduction
C5H4(SiMe3) [13] and trans-RuX(C„CC„CFc)(dppe)2
(X = Cl, C„CC6H4NO2-4, C„CFc, C„CC„CFc) [14].
An early approach of ours involved the syntheses of
Fc(C„C)nW(CO)3Cp (n = 1–4), but the lack of any mea-
surable electrochemical response of the tungsten end-cap
precluded assessment of any electronic communication
between the two centres [15]. Detailed studies of the reac-
tions of FcC„CC„CFc with ruthenium cluster carbonyls
have been reported [16], while the syntheses and structures
of a series of osmium cluster carbonyls derived from
Fc(C„C)nFc (n = 2, 4, 6) together with some of their elec-
trochemical properties have also been described [17]. Other
cluster-bonded poly-ynylferrocene ligands include com-
plexes obtained from the triosmium cluster and 1,10-
(Me3SiC„C)2Fc0 [Fc0 = ferrocene-1,10-diyl, Fe(g-C5H4-)2]
[18]. We and others have described some of the chemistry
associated with complexes Fc(C„C)nRu(PP)Cp0 [n = 1,
2; PP = dppe, Cp0 = Cp, Cp*; PP = (PPh3)3, Cp0 = Cp]
and the 1,10-bis(ethynyl)ferrocene complexes of the type
Fc0-1,10-{C„CRu(PP)Cp}2 [19,20]. The present account
is devoted to the third member of this series, of
Poly-unsaturated carbon chains have evinced much
interest as models for molecular wires for the design and
construction of molecular-scale electronic devices [1–3].
To function in this way, there must be evidence for elec-
tronic communication through such ‘‘wires’’ and to this
effect, several groups have studied compounds wherein
the poly-yne chains are end-capped with redox-active
groups. Examples containing manganese [4], rhenium [5],
iron [6,7], ruthenium [8,9], rhodium [10] and platinum
[11] have been studied extensively, many of these being
summarised in recent reviews [12].
A well-known redox-active organometallic fragment is
the ferrocenyl group (Fc). The few accounts of ferrocenyl-
poly-ynes end-capped with r-bonded transition metal frag-
ments available include studies of TiX(C„CC„CFc)CpSi
(X = Cl, C„CFc, C„CRc, C„CC„CFc); CpSi = g-
*
Corresponding author. Fax: +61 8 8303 4358.
E-mail address: michael.bruce@adelaide.edu.au (M.I. Bruce).
0022-328X/$ - see front matter ꢀ 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2007.02.043

M.I. Bruce et al. / Journal of Organometallic Chemistry 692 (2007) 2564–2574
2565
which we have studied the molecule Fc(C„C)3-
Ru(dppe)Cp.
assign to Ca attached to Ru. Other resonances at d 65.91,
69.34, 70.71, 74.85 and 94.40 are tentatively assigned
to the other atoms of the C6 chain. The assignment of
carbon resonances in poly-yne chains end-capped by vari-
ous groups has been a matter of debate for some time. In
an account of the poly-ynes Ar(C„C)nAr [Ar = 3,5-
(TBDMS-O)2C6H3, n = 2, 4, 6, 8, 10], it was pointed out
that elongation of the chain resulted in new signals appear-
ing in the range d 62–65, whilst an earlier suggestion by the
same group was that the expected chemical shift of carbyne
[–(C„C)n–] would be a broad signal at d 63–64 [22]. The
C6 chain resonances for Fc(C„C)3Fc occur at d 65.8,
79.3 and 72.1, which have been assigned to C(1,2,3), respec-
tively [numbering is from the Fc–C(1) atom] [23]. For
{Cp*(dppe)Ru}2{l-(C„C)4} (the C6 complex is not solu-
ble enough to give a resolved 13C NMR spectrum) the C4
chain carbons are found at d 51.12, 63.60, 92.54 and
94.58t [J(CP) = 22 Hz] and have been assigned to
C(1,2,3,4), respectively [20a]. For Ru{(C„C)nFc}(dp-
pe)Cp*, we have reported the chain carbon resonances at
d 69.81, 77.77, 95.19 and 115.75t [J(CP) = 25.2 Hz]
(n = 2) [19a] and at d 65.91, 69.34, 70.71, 74.85, 94.40
and 123.13t [J(CP) = 22.0 Hz] (n = 3, 2). On the basis of
these values, we are inclined to assign the resonance of
the carbon atom attached to Ru as being at lowest field
and showing coupling to 31P, other carbons in the chain
being found at progressively higher field. The resonance
for the carbon attached the Fc group is likely to be one
of the signals found between d 65.9 and 74.85.
2. Results and discussion
The triyne Fc(C„C)3SiMe3 (1; Scheme 1) was obtained
in 78% yield by dehydrochlorination of cis-FcC
„CC„CCH@CHCl with LiNiPr2, followed by quenching
of the resulting lithiated triyne with SiClMe3. It formed a
dark orange oil which was not fully characterised on
1
account of its instability. Nevertheless, the H [singlets at
d 0.22 (SiMe3), 4.26 (Cp) and multiplets at d 4.29–4.30,
4.54–4.56 (C5H4)] and 13C NMR spectra [d ꢀ0.48 (SiMe3),
70.35 (Cp) and several signals between d 61.69 and 88.54
arising from the C5H4 and „C carbons], together with ions
at m/z 330 and 258, assigned to M+ and [MꢀSiMe3]+,
respectively, are consistent with its formulation.
Coupling of 1 with RuCl(dppe)Cp in MeOH containing
a small amount of water, a drop of dbu and KF afforded
Fc(C„C)3Ru(dppe)Cp (2) in 53% yield as a dark orange
solid. This complex was fully characterised by elemental
analyses, its spectroscopic properties and by a single-crys-
tal X-ray structure determination (see below). The IR spec-
trum contains two m(C„C) bands at 2108 and 1992 cmꢀ1
,
while the ES-MS, obtained from a MeOH solution con-
1
taining NaOMe, contains [M+Na]+ at m/z 845. The H
NMR spectrum contains resonances characteristic of the
Fc [d 3.93 (Fe–Cp), multiplets at d 3.76 and 4.23 (C5H4)],
dppe (CH2 and Ph multiplets at d 1.80–2.00 and 2.30–
2.50, and 6.85–7.87) and the Ru–Cp singlet at d 4.58, and
the dppe ligands give rise to a 31P resonance at d 85.2 (cf.
d 86.0 in Ru(C„CC„CFc)(dppe)Cp [19a], d 79.4 in
{Cp*(dppe)Ru}2{l-(C„C)3} [21]).
2.1. Electrochemistry
The series Ru{(C„C)nFc}(dppe)Cp (n = 1–3) have now
been prepared and it is of interest to compare their electro-
chemical responses. Under similar conditions (see Section
4) all three complexes show two oxidation processes, one
irreversible at +0.14, +0.32 and +0.50 V (for n = 1, 2, 3,
respectively) and a reversible process at +0.72, +0.76 and
In the 13C NMR spectrum, resonances at d 69.69 and
83.13 (for the Fe–Cp and Ru–Cp groups, respectively),
multiplet signals at d 27.4–28.3 (dppe–CH2), 65.9 and
68.2 (C5H4) and between 129 and 142 (Ph) were accompa-
nied by a triplet at d 123.13 [J(CP) = 22 Hz], which we
Cl
CH
i, ii
Fc
C
C
C
C
CH
Fc
C
C
C
C
C
C
SiMe3
(1)
iii
Fc
C
C
C
C
C
C
Ru
Ph2P
PPh2
(2)
Scheme 1. Reagents: (i) LiNiPr2; (ii) SiClMe3; (iii) RuCl(dppe)Cp, KF, dbu.

2566
M.I. Bruce et al. / Journal of Organometallic Chemistry 692 (2007) 2564–2574
+0.73 V (for n = 1, 2, 3, respectively). The diyne (n = 2)
also shows a quasi-reversible oxidation at +0.94 V. The rel-
ative insensitivity of the higher oxidation to the carbon
chain length suggests that it is associated with the ferrocene
moiety, whereas the increase in oxidation potential of the
lower energy process with increasing chain length suggests
that it is associated with the ruthenium centre, reflecting an
increase in transfer of electron density to the carbon chain.
for 3, while that of 4 has an AB quartet at d 66.4/81.8 from
the different P nuclei which result from the asymmetry of
the cyanocarbon ligand. In their 13C NMR spectra, two
multiplets are similarly found for the dppe CH2 groups in
4, compared with only one in 3. Other major differences
relate the presence of resonances assigned to the cyclobute-
nyl sp3 carbons in 3 at d 84.43 and 86.57, and one of the sp2
carbons at d 148.92; other skeletal carbons of the cyanocar-
bon ligand were not resolved. In contrast, the spectrum of 4
contained several signals between d 70.0 and 97.39, of
which those at d 71.24, 73.45d, 77.20, 81.27. 95.72d,
96.87, 97.39 are assigned to skeletal carbons (by compari-
son with the spectra of related complexes obtained from
FcC„CC„CRu(PP)Cp0 [19]), and at d 163.63, which is
assigned to C–Ru.
We note that
W{(C„C)nFc}(CO)3Cp (n = 1–4) showed
a
previous study of the complexes
similar
a
increase in oxidation potential with increasing chain length,
each added C„C unit resulting in an approximate 0.06 V
increase in oxidation potential [15b]. However, in this case,
the processes are reversible and the changes result from
partial electron transfer to the carbon chain from the ferro-
cene centre.
Addition of Co2(CO)8 to the triyne 2 afforded the bis-
adduct FcC2{Co2(CO)6}C2{Co2(CO)6}C„CRu(dppe)Cp
(5) as a dark purple solid in 65% yield (Scheme 3). There
was no evidence for the presence of either the mono- or
tris-adduct, although formation of the latter is not antici-
pated, since similar complexes of other poly-ynes contain
a maximum of two adjacent C2Co2(CO)6 fragments in
the chains [24]. Characterisation of 5 included elemental
analyses and the ES-MS of a solution containing NaOMe,
which has ions at m/z 1417 and 1391, assigned to [M+Na]+
and M+, respectively. Only terminal m(CO) bands are pres-
ent in the IR spectrum between 2091 and 2011 cmꢀ1, while
2.2. Reactions of Fc(C„C)3Ru(dppe)Cp (2)
The triyne 2 showed the expected reactivity towards the
electron-deficient alkene C2(CN)4 (tcne), binuclear cobalt
carbonyls and Os3(CO)10(NCMe)2 (Schemes 2–4). With
the cyanoalkene, a mixture of green cyclobutenyl (3) and
dark blue dienyl (4) complexes was successfully separated,
the latter being shown to have formed by addition to the
C„C triple bond adjacent to the ruthenium centre by an
X-ray structural determination (Scheme 2). The cyclobute-
nyl 3 was converted into 4 by heating in benzene for several
hours, there being no evidence for the formation of any
other product. The IR spectrum of 3 contains bands
assigned to m(CN) at 2226 and 2207 and to m(C„C) at
2181 and 2135 cmꢀ1, while that of 4 has m(CN) at 2208
and m(C„C) at rather lower frequencies than 3, at 2163
and 1978 cmꢀ1. The 1H NMR spectra of both isomers
are similar and contain no distinguishing features. The
31P NMR spectra contain a singlet resonance at d 85.4
1
the H NMR spectrum contains singlet resonances at d
4.22 (Cp–Fe) and 4.80 (Cp–Ru), together with other signals
arising from the C5H4 (d 4.40, 4.66) and dppe groups (d
2.56, 2.78 and 7.02–7.76). In the 13C NMR spectrum, sig-
nals at d 69.74 (Cp–Fe) and 83.68 (Cp–Ru) are accompa-
nied by several others in the region d 68.35–108.87
(assigned collectively to the C5H4 and carbon chain nuclei),
multiplets from the dppe–CH2 and Ph groups (d 26.90–
28.12 and 127.90–142.40, respectively) and a triplet
Fc
C
C
C
Ph2
P
Ru
C
C
C
PPh2
(NC)2C
C(CN)2
tcne
(3)
Ru
C
C
C
C
C
C
Fc
Ph2P
C6H6, reflux
PPh2
C(CN)2
Fc
C
C
C
C
C
Ru
C
Ph2P
PPh2
C(CN)2
(4)
Scheme 2.

M.I. Bruce et al. / Journal of Organometallic Chemistry 692 (2007) 2564–2574
2567
Fc
Co(CO)3
C
C
Co(CO)3
Co(CO)3
C
Ru
C
C
C
Co2(CO)8
Ph2P
PPh2
(OC)3Co
(5)
Ru
C
C
C
C
C
C
Fc
Ph2P
Co2(μ-dppm)(CO)6
PPh2
Fc
C
Co(CO)2
PPh2
C
Ru
C
C
C
C
Ph2P
(OC)2Co
PPh2
P
Ph2
(6)
Scheme 3.
ES-MS, which contains M+ at m/z 1436. The IR spectrum
contains a m(C„C) band at 2113 cmꢀ1 together with termi-
nal m(CO) absorptions between 2009 and 1945 cmꢀ1. In the
NMR spectra, characteristic signals for the Cp–Fe (dH
4.41, dC 69.30) and Cp–Ru (dH 4.71, dC 83.25) were accom-
panied by several multiplets arising from the dppe, dppm
and C5H4 ligands. Also present were peaks at d 91.74,
125.99, 134.37 and 138.60 all showing triplet couplings to
phosphorus, together with two Co–CO multiplet reso-
nances at d 202.22 and 206.68.
Ru
C
C
C
C
C
C
Fc
Ph2P
PPh2
Os3(CO)10(NCMe)2
Fc
C
Purple crystalline Os3{l3-C2C„CC„C[Ru(dppe)-
Cp]}(CO)10 (7) was obtained in 25% yield from a reaction
between triyne 2 and Os3(CO)10(NCMe)2 carried out in
thf at r.t. for 1 h (Scheme 4). The molecular structure was
determined from a single-crystal X-ray study, both analyti-
cal data and the ES-MS ([M+OMe]ꢀ at m/z 1704) being
consistent with the solid state structure. The IR spectrum
containeꢀd1 both terminal m(CO) bands (between 2092 and
Os(CO)3
Os(CO)4
Ru
C
C
C
C
C
Ph2P
PPh2
(OC)3Os
(7)
CHCl3
2000 cm
)
and
a
bridging m(CO) absorption at
1821 cmꢀ1, likely arising from the two semi-bridging CO
ligands found in the crystal structure. A single band at
2128 cmꢀ1 is assigned to a m(C„C) mode. In the NMR
spectra, Cp–Fe (dH 4.23, dC 70.5) and Cp–Ru (dH 4.60, dC
83.95) singlets are accompanied by resonances from the
dppe and C5H4 ligands and a broad singlet at dC 179.16
for the Os–CO groups. Several singlets between d 53.7
and 152.9 arise from the chain carbons, although it has
not been possible to assign these with confidence.
(CO)4
Os
Fe
H
C
C
C
C
C
C
Os
Os(CO)3
Ru(dppe)Cp
(CO)3
(8)
Scheme 4.
On allowing a solution in chloroform to stand for seven
days at r.t., complex 7 was transformed into brown crystal-
line 8 which has only been partially characterised. The
presence of terminal (2092–1990 cmꢀ1) and bridging
(1815 cmꢀ1) m(CO) bands indicates the preservation of
the Os3 cluster, also supported by [M+H]+ appearing in
the ES-MS at m/z 1673. In the absence of an X-ray deter-
mination, we can only speculate on the molecular structure,
[J(CP) = 24.0 Hz] at d 156.74, assigned to C(1) attached to
the ruthenium centre and indicating that this carbon is not
attached to a Co2(CO)6 group. The Co–CO groups give a
broad signal at d 199.57.
In contrast, only mono-adduct 6 was obtained from the
reaction between 2 and Co2(l-dppm)(CO)6. The composi-
tion is indicated by the elemental analysis and the

2568
M.I. Bruce et al. / Journal of Organometallic Chemistry 692 (2007) 2564–2574
which we suspect involves further metallation of the C5H4
ring of the ferrocenyl moiety. Singlet resonances (dH 3.78
and 4.72, dC 69.19 and 82.88) confirm the retention of
the Cp–Fe and Cp–Ru moieties, and only three substituted
C5 ring protons are found at d 3.72, 4.16 and 4.26. Three of
the corresponding carbons resonate at d 64.25, 66.75 and
67.61. The presence of a single proton resonance at d
6.29 is consistent with the H atom being transferred to
the carbon chain rather than to the cluster (there is no
high-field resonance characteristic of a cluster-bonded pro-
ton). The separation of the 31P NMR resonance of 8 into
an AB quartet suggests that a degree of asymmetry has
arisen near to the ruthenium centre. Considering the above
data, we are inclined to suggest a structure similar to 9
(Chart 1), proposed as an intermediate on the way to one
of the products isolated from the reaction of Fc(C„C)4Fc
with Os3(l-H)2(CO)10 [17e]. The complex may also be
related to Os3(l-H){l3-C(SiMe3)CMeCHC[(g-C5H3)-
FeCp]}(CO)8 (10), containing a cyclometalated ferrocenyl
group, recently described as being obtained by thermolysis
of Os3{l3-C(SiMe3)CMeCHCFc}(CO)9 in refluxing ben-
zene [25]. In the present case, if migration of the proton
occurs first to the Os3 cluster, further migration of this pro-
ton to the C6 chain then takes place.
602’
601’
603’
604’
112
602
Fe
603
605’
122
1
121
P(1)
6
111
5
4
601
101
3
604
605
2
102
210
Ru
105
104
221
P(2)
211
212
222
Fig. 1. Projection of a molecule of Ru(C„CC„CC„CFc)(dppe)Cp (2).
605’
604’
605
601’
Fe
603’
601
6
CN(2102)
CN(2101)
112
122
Molecular structures. Molecules of 2, 4, 6 and 7 are
depicted in Figs. 1–4, while significant bond parameters
are collected in Table 1; in all cases, one formula unit of
the substrate, devoid of crystallographic symmetry,
comprises the asymmetric unit of the structure. All contain
the familiar Ru(dppe)Cp end-cap, the geometries of which
resemble those of the many other examples recorded in the
Cambridge Data Base. In the present compounds, the
5
602’
121
4
210
602
3
P(1)
102
111
2
101
10
Ru
1
20
CN(1102)
110
105
222
103
˚
104
221
Ru–P distances range between 2.260 and 2.309(3) A, the
P(2)
˚
Ru–C(cp) distances are between 2.185 and 2.273(6) A
211
CN(1101)
˚
(averages 2.23–2.25 A) and the P(1)–Ru–P(2) and P(1,2)–
212
Ru–C(1) angles are between 82.7ꢁ and 84.03(8)ꢁ, and
83.8ꢁ and 102.4(3)ꢁ, respectively. Similarly, the ferrocenyl
moieties show no unusual features, with average Fe–
˚
C(cp) distances of between 2.01 and 2.05 A, with the
˚
C(6)–C(601) bonds being between 1.40 and 1.47(2) A.
Fig. 2. Projection of
a molecule of Ru{C[@C(CN)2]C[C@C(CN)2]-
C„CC„CFc}(dppe)Cp (4).
(CO)4
Os
Fe
H
C
(C
C
C)3
In 2, the Ru–C„C–C„C–C„C–Fc chain shows an
Fc
(OC)3Os
Os(CO)3
alternating short–long–short–long–short C–C bond
(9)
˚
pattern [short, 1.212–1.217(7), long 1.371, 1.374(7) A],
˚
with an Ru–C(1) separation of 1.986(4) A. Angles at
(CO)3
Os
SiMe3
the individual carbons range between 173.1ꢁ and 177.0
(5)ꢁ. Since there are no intermolecular contacts between
these carbons and other atoms, the usual explanation
of a weak bending moment for the C–C bonds affected
by the crystal environment probably applies in this case
also [26]. Comparison with the recently reported
structure of Fc(C„C)3Fc [23] shows little difference in
the C–C bond lengths [short, 1.211(1), 1.215(1), long
H
Fe
C
C
(CO)2
Os
(OC)3
Os
C
Me
C
H
(10)
Chart 1.

M.I. Bruce et al. / Journal of Organometallic Chemistry 692 (2007) 2564–2574
2569
CO(12)
CO(33)
Os(1)
CO(11)
122
604
CO(13)
6
122
605
311
112
111
412
121
P(1)
411
30
111
10
312
Os(3)
CO(31)
121
102
602
601
322
321
P(1)
CO(24)
CO(21)
Fe
4
421
P(4)
422
3
112
101
102
5
CO(31)
CO(41)
2
10
Os(2)
Ru
Co(3)
101
103
CO(23)
103
20
605’
601’
3
Co(4)
1
4
Ru
602’
20
1
212
2
105
211
5
CO(22)
104
105
6
CO(32)
601’
CO(42)
P(2)
104
P(2)
212
221
601
211
222
605
222
602
603
Fe
221
604
605’
603’
604’
Fig. 4. Projection of a molecule of Os3{l3-C2C„CC„C[Ru(dppe)Cp]}-
(CO)10 (7).
Fig. 3. Projection of
a
molecule of Ru{C„CC„CC2Fc[Co2(l-
dppm)(CO)4]}(dppe)Cp (6).
Table 1
Selected bond distances (A) and angles (ꢁ)
˚
Complex
2
4
6
7
˚
Bond distances (A)
Ru(1)–P(1)
Ru(1)–P(2)
Ru(1)–C(cp)
Ru(1)–C(cp)
(av.)
2.260(1)
2.262(1)
2.229(5)–2.252(5)
2.242(9)
2.266(3)
2.309(3)
2.185(13)–2.263(12)
2.23(3)
2.244(2)
2.250(2)
2.222(6)–2.263(8)
2.247(17)
2.264(2)
2.261(2)
2.237(11)–2.273(6)
2.251(15)
Ru(1)–C(1)
C(1)–C(2)
1.986(4)
1.212(6)
2.018(11)
1.49(2)
1.989(5)
1.222(7)
1.983(8)
1.24(1)
C(2)–C(3)
1.371(6)
1.37(2)
1.363(6)
1.37(1)
C(3)–C(4)
1.217(7)
1.20(2)
1.232(6)
1.22(1)
C(4)–C(5)
1.374(7)
1.34(2)
1.390(6)
1.43(1)
C(5)–C(6)
1.214(7)
1.20(2)
1.359(6)
1.44(1)
C(6)–C(601)
Fe–C(cp)
1.415(7)
2.024(5)–2.045(5), 2.026(5)–
2.046(5)
1.40(2)
1.452(6)
2.026(6)–2.061(5), 2.004(6)–
2.048(6)
1.47(1)
1.978(14)–2.035(14), 1.999(17)–
2.013(15)
2.033(7)–2.055(9), 2.032(8)–
2.049(14)
Fe–C(cp) (av.)
2.036(9), 2.038(7)
2.01(2), 2.007(6)
2.046(12), 2.03(2)
2.045(11), 2.040(7)
Bond angles (ꢁ)
P(1)–Ru(1)–
P(2)
P(1)–Ru(1)–
C(1)
P(2)–Ru(1)–
C(1)
Ru(1)–C(1)–
C(2)
83.66(4)
81.8(1)
90.1(1)
174.3(4)
82.7(1)
102.4(3)
90.0(3)
118.6(8)
83.86(5)
85.2(2)
84.6(2)
175.8(5)
84.03(8)
83.8(2)
87.7(2)
175.7(7)
C(1)–C(2)–C(3)
C(2)–C(3)–C(4)
C(3)–C(4)–C(5)
C(4)–C(5)–C(6)
C(5)–C(6)–
C(601)
173.1(5)
176.5(5)
175.3(5)
176.3(5)
177.0(5)
121.7(11)
172.6(13)
178.4(14)
176.8(15)
178.0(15)
177.1(6)
177.7(6)
168.5(4)
144.6(4)
140.5(4)
171.1(9)
172.4(9)
178.2(8)
125.9(7)
122.9(7)
˚
For 4: C(1)–C(110) 1.35(2), C(2)–C(210) 1.40(2), C(n10)–CN 1.37(2)–1.42(2), C–N 1.14(2)–1.16(2) A; Ru, C(2)–C(1)–C(110) 126.9(9)ꢁ, 114.0(10)ꢁ, C(1,3)–
C(2)–C(210) 117.8(10)ꢁ, 120.4(11)ꢁ, C(n101)–C(n10)–C(n102) 114.1(10)ꢁ, 116.4(11)ꢁ (only Ru, Fe, Cl, P were refined with anisotropic Uij).
˚
For 6: Co(3)–Co(4) 2.458(1), Co(3)–P(3) 2.202(1), Co(4)–P(4) 2.217(1), Co(3)–C(5,6) 1.978(5), 1.958(5), Co(4)–C(5,6) 1.997(4), 1.943(5) A.
For 7: Os(1)–Os(2,3) 2.8281(11), 2.7307(8), Os(2)–Os(3) 2.8689(11), Os(1)–C(5,6) 2.209(8), 2.343(7), Os(2)–C(5) 2.158(7), Os(3)–C(6) 2.108(8) A.
˚
˚
˚
1.362(1) A], although the bending of the chain is
1.4182(13) A for C(1)–C(11) in Fc(C„C)3Fc [23]]. The
considerably less [angles at C(2,3) 178.9(1)ꢁ, 179.7(1)ꢁ,
solvation comprises columns of centrosymmetric benzene
molecules stacked face-to-edge up a.
˚
respectively]. The C(6)–C(601) distance is 1.415(7) A [cf.

2570
M.I. Bruce et al. / Journal of Organometallic Chemistry 692 (2007) 2564–2574
The molecule of 4 contains a tetracyanobuta-1,3-dienyl
were taken during subsequent work-up. Common solvents
˚
ligand attached to Ru [Ru–C(1) 2.018(11) A], in which the
two C@C(CN)2 groups have taken up an s-trans conforma-
tion, in common with the majority of other structurally
determined examples of this class of compound, such as
Ru{C[@C(CN)2]CPh@C(CN)2}(dppe)Cp [27], but with
the notable exceptions of PtCl{C[@C(CN)2CPh@C(CN)2}-
(PEt3)2 and {PtCl(PMe3)2}2{l-C[@C(CN)2]C[C@C(CN)2]},
in which the cyano-diene ligands adopt the s-cis conforma-
tion [28]. Atom C(2) is attached to the diynyl chain in which
the C„C triple bonds are localised [C(2)ꢁ ꢁ ꢁC(6) separations
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
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
were dissolved in CDCl3 contained in 5 mm sample tubes.
Chemical shifts are given in ppm relative to internal tetra-
˚
1.37, 1.20, 1.34, 1.20(2) A]. Angles at C(1) and C(2)
118.6(8), 121.7(11)ꢁ] are consistent with their sp2 hybridisa-
tion, while those at C(3)–C(6) [172.6–178.4(14)ꢁ] reflect the
C(sp) constituents. The structure confirms the site of addi-
tion of the cyanoalkene at the C„C triple bond adjacent
to the Ru centre, suggesting that this bond is more activated
than that adjacent to the Fc nucleus. Many examples of
addition of cyano-alkenes to alkynyl-metal complexes con-
taining a r-bonded alkynyl ligand have been described
[27,29,30], but it is only recently that similar reactions with
a diynyl-ferrocene have been reported [31].
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 [32]. Electrochemical sam-
ples (1 mM) were dissolved in CH2Cl2 containing 0.5 M
[NBu4]BF4 as the supporting electrolyte. Cyclic voltammo-
grams were recorded using a PAR model 263 apparatus,
with a saturated calomel electrode, with a Pt-mesh working
electrode, Pt wire counter and pseudo-reference electrodes.
Ferrocene was used as an internal calibrant (FeCp2/
[FeCp2]+ = +0. 46 V). Elemental analyses were by CMAS,
Belmont, Vic., Australia.
The structures of 6 and 7 show that the additions of the
Co2 or Os3 fragments have occurred at the C„C triple
bond adjacent to the Fc group. Along the carbon chain,
the bond distances Ru–C(1), C(1)–C(2), C(2)–C(3), C(3)–
C(4), C(4)–C(5) are 1.989(5), 1.222(7), 1.363(7), 1.232(6),
˚
1.390(6) A for 6 and 1.983(8), 1.24(1), 1.37(1), 1.22(1),
˚
1.43(1) A for 7, all consistent with preservation of the diyn-
yl-ruthenium structure. Lengthening of the C(5)–C(6) bond
˚
˚
[to 1.359(6) A in 6, 1.44(1) A for 7] reflects the usual effect
of 2p-coordination to the Co2 or 2r,p-coordination to the
Os3 cluster. This is accompanied by bending of the chain at
these atoms, which is less for 6 than for 7, as expected
[C(4)–C(5)–C(6) 144.6(4)ꢁ, 125.9(7)ꢁ; C(5)–C(6)–C(601)
140.5(4)ꢁ, 122.9(7)ꢁ for 6 and 7].
4.3. Reagents
The compounds FcC„CC„CCH@CHCl-cis [17d],
RuCl(dppe)Cp [33], Co2(l-dppm)(CO)6 [34] and
Os3(CO)10(NCMe)2 [35] were made by the cited methods.
3. Conclusions
The synthesis of triyne Fc(C„C)3Ru(dppe)Cp (2) has
been achieved, together with addition of tcne, Co2(l-
dppm)n(CO)6ꢀ2n (n = 0, 1) and Os3(CO)10 fragments to
the C6 chain. Whereas the cyanoalkene adds to the C„C
triple bond more activated by the Ru(dppe)Cp group,
i.e., in an electronically controlled reaction, the bi- and
tri-nuclear metal fragments add to the sterically most
accessible C„C triple bond adjacent to the Fc group. In
solution, the Os3 cluster complex undergoes a still relatively
rare metallation of the ferrocenyl group with migration of
the H atom to the carbon chain.
4.4. Fc(C„C)3SiMe3 (1)
cis-FcC„CC„CCH@CHCl (1320 mg, 4.47 mmol) was
added to a solution of LiNiPr2 (9.8 mmol) in dry ether at
ꢀ78 ꢁC and the mixture was stirred for 4 h. After warming
briefly to room temperature, the mixture was again cooled
to ꢀ78 ꢁC and quenched with an excess of SiClMe3. Sol-
vent was removed under vacuum and a diethyl ether extract
was purified by passage through a pad of silica before
removing solvent to give Fc(C„C)3SiMe3 (1) as an unsta-
ble dark orange oil (1150 mg, 78%). No elemental analysis
was possible because of its instability.
4. Experimental
IR (nujol): m(C„C) 2187s, 2165s, 2070s cmꢀ1 1H
.
NMR: d 0.22 (s, 9H, SiMe3), 4.26 (s, 5H, Cp), 4.29–4.30,
4.54–4.56 (2 · m, 2 · 2H, C5H4). 13C NMR: d ꢀ0.48
(SiMe3), 61.69, 62.68, 64.33, 69.79 (C5H4), 70.35 (Cp),
70.78, 72.73, 78.18, 87.69, 88.54. ES-MS (MeOH, positive
ion, m/z): 330, M+; 258, [MꢀSiMe3]+.
4.1. General
All reactions were carried out under dry nitrogen,
although normally no special precautions to exclude air

M.I. Bruce et al. / Journal of Organometallic Chemistry 692 (2007) 2564–2574
2571
4.5. Fc(C„C)3Ru(dppe)Cp (2)
other bands at 1584w, 1573w, 1537m (sh), 1531m cmꢀ1
1H NMR:
2.40–2.65, 2.85–3.10 (2 · m, 2 · 2H,
.
d
A degassed solution of Fc(C„C)3SiMe3 (1011 mg,
3.04 mmol) in MeOH (50 ml) containing water (0.5 ml)
and dbu (1 drop) was added to a stirred mixture of
RuCl(dppe)Cp (1880 mg, 3.13 mmol) and KF (272 mg,
4.70 mmol). After heating at reflux point for 1 h and cool-
ing, the resulting precipitate was collected, dried in vacuum
and purified by column chromatography (basic alumina,
benzene) to give Fc(C„C)3Ru(dppe)Cp (2) (1365 mg,
53%) as a dark orange solid. Anal. Calc. for C47H38Fe-
P2Ru: C, 68.70; H, 4.66. Found: C, 68.67; H, 4.71%. M,
822. IR (nujol): m(C„C) 2108s, 1992s; other bands at
2 · CH2), 4.37 (s, 5H, Cp–Fe), 4.60, 4.69 (2 · m, 2 · 2H,
C5H4), 5.02 (s, 5H, Cp–Ru), 7.20–7.26, 7.33–7.43, 7.68–
7.72 (3 · m, 4H + 12H + 4H, Ph). 13C NMR: d 28.42–
28.73 (m, CH2), 60.56 (Fc ipso), 71.21 (Cp–Fe), 72.25,
73.40 (2 · C5H4), 84.43, 86.57 [2 · C(sp3) of cyclobutene],
86.26 (Cp–Ru), 112.07, 113.88, 115.42, 116.54, 119.77
(4 · CN + C), 128.04–128.43, 129.71, 130.29, 130.94–
131.08, 133.46–133.60 (6 · m, Ph), 134.89–134.23, 139.80–
140.35 (2 · m), 148.92 (C@C). 31P NMR: d 85.4 (dppe).
ES-MS (MeOH, positive ion, m/z): 973, [M+Na]+.
(b) With Co2(CO)8. A solution of Fc(C„C)3Ru(dp-
pe)Cp (35 mg, 0.043 mmol) and Co2(CO)8 (135 mg,
0.38 mmol) in dry thf (5 ml) was stirred overnight. After
removal of solvent in vacuum, the residue was purified by
preparative TLC (hexane/acetone 2/1) to give Fc{C2[Co2-
(CO)6]}2C„CRu(dppe)Cp (5) as a dark purple solid
(39 mg, 65%). Anal. Calc. for C59H38Co4FeO12P2Ru: C,
50.85; H, 2.75. Found: C, 50.96; H, 2.69%. M, 1394. IR
(CH2Cl2): m(CO) 2091w, 2070m, 2051s, 2044s (sh), 2023s
1
1585w, 1571w cmꢀ1. H NMR (C6D6): d 1.80–2.00, 2.30–
2.50 (2 · m, 2 · 2H, CH2), 3.76–3.77, 4.23–4.24 (2 · m,
2 · 2H, C5H4), 3.93 (s, 5H, Cp–Fe), 4.58 (s, 5H, Cp–Ru),
6.85–7.00, 7.05–7.30, 7.81–7.87 (3 · m, 7H + 8H + 5H,
Ph). 13C NMR: d 27.40–28.32 (m, 2 · CH2), 65.91, 68.17
(C5H4), 69.34, 69.69 (Cp–Fe), 70.71, 71.82 (C5H4), 74.85,
83.13 (Cp–Ru), 94.40, 123.13 [t, J(CP) 22.0 Hz], 129.47,
131.26–131.47, 133.27–134.48, 135.76–136.78, 141.02–
141.79 (5 · m, Ph). 31P: d 85.23 (dppe). ES-MS (MeOH +
NaOMe, positive ion, m/z): 845, [M+Na]+.
1
(sh), 2011s; other band at 1435w cmꢀ1. H NMR: d 2.56,
2.78 [2 · s (br), 2 · 2H, CH2], 4.22 [s (br), 5H, Cp–Fe],
4.40, 4.66 [2 · s (br), 2 · 2H, C5H4], 4.80 (br s, 5H, Cp–
Ru), 7.02–7.30, 7.76 (2 · m, 16H + 4H, Ph). 13C NMR: d
26.90–28.12 (m, CH2), 68.35, 71.36 (2 · m, C5H4), 69.74
(s, Cp–Fe), 83.68 (s, Cp–Ru), 88.09, 88.64, 89.39, 98.30,
98.88, 108.87, 127.90–128.17, 128.75, 131.06–131.12,
133.58–133.72, 136.19–136.87, 141.87–142.40 (6 · m, Ph),
156.74 [t, J 24.0 Hz, Ca], 199.57 (CO). 31P NMR: d 86.79
(dppe). ES-MS (MeOH, positive ion, m/z): 1417,
[M+Na]+; 1394, M+.
4.6. Reactions of Fc(C„C)3Ru(dppe)Cp
(a) With tcne. A mixture of Fc(C„C)3Ru(dppe)Cp
(104 mg, 0.127 mmol) and tcne (19 mg, 0.15 mmol) in dry
CH2Cl2 (5 ml) was sonicated at r.t. for 8 h. Removal of sol-
vent in vacuum and purification by preparative TLC
(CH2Cl2) gave FcC„CC„C{C[@C(CN)2]}2Ru(dppe)Cp
(3) as a dark blue solid (Rf = 0.3; 12 mg, 10%). The base-
line material was recovered and extracted several times
with diethyl ether and purified by a second TLC (5%
acetone-CH2Cl2) to give the green cyclobutenyl complex
FcC„CC„C{C@CC(CN)2C(CN)2}Ru(dppe)Cp (4) (Rf =
0.3; 50 mg, 41%).
(c) With Co2(l-dppm)(CO)6.
A
solution of
Fc(C„C)3Ru(dppe)Cp (38 mg, 0.046 mmol) and Co2-
(l-dppm)(CO)6 (39 mg, 0.58 mmol) in dry thf (20 ml) ws
heated at reflux point overnight. After removal of solvent
under vacuum, preparative TLC of the residue (hexane/
acetone 3/2) afforded the mono adduct FcC2{Co2(l-
dppm)(CO)4}C„CC„C Ru(dppe)Cp (6) as a brown solid
(60 mg, 91%). Anal. Calc. for C76H60Co2FeO4P4Ru: C,
63.57; H, 4.21. Found: C, 63.41; H, 4.09%. M, 1436. IR
(CH2Cl2): m(CC) 2113w; m(CO) 2009m, 1992s, 1964m,
For 3: Anal. Calc. for C53H38FeN4P2Ru: C, 67.02; H,
4.03; N, 5.90. Found: C, 67.08; H, 3.93; N, 5.96%. M,
950. IR (CH2Cl2): m(C„N) 2226w, 2207w; m(C„C)
2181s, 2135w; other bands at 1605m, 1502m cmꢀ1 1H
.
NMR: d 2.30–2.50, 2.50–2.70 (2 · m, 2 · 2H, CH2), 4.31
(s, 5H, Cp–Fe), 4.42 [m (br), 2H, C5H4], 4.62, 4.66
(2 · m, 2 · 1H, C5H4), 4.93 (s, 5H, Cp–Ru), 6.63–6.69,
7.12–7.34, 7.50–7.73, 7.97–8.03 (4 · m, Ph). 13C NMR: d
26.28–26.96, 29.02–29.67(2 · m, CH2), 60.75 (C5H4 ipso),
70.01, 71.01 (Cp–Fe), 71.24, 72.18, 73.24, 73.45 [d, J(CP)
3.2 Hz], 77.20, 81.27, 86.04 (Cp–Ru), 95.72 [d, J(CP)
6.8 Hz], 96.87, 97.39, 111.93, 112.36, 112.88, 118.12
(4 · CN), 127.78–128.24, 128.64–128.76, 130.54, 131.26–
131.74 (4 · m, Ph), 134.52, 135.03, 136.13, 136.72, 140.07,
140.49, 163.63 (C@C). 31P NMR: d 66.4 [d, J(PP)
22.2 Hz], 81.8 [d, J(PP) 22.2 Hz]. ES-MS (MeOH +
NaOMe, positive ion, m/z): 973, [M+Na]+.
1945w; other band at 1435w cmꢀ1 1H NMR: d 1.95–
.
2.15, 2.60–2.80 (2 · m, 2 · 2H, 2 · CH2 of dppe), 2.95–
3.15, 3.70–3.85 (2 · m, 2 · 1H, CH2 of dppm), 4.16 (m,
2H, C5H4), 4.41 (s, 5H, Cp–Fe), 4.71 (m, 7H,
C5H4 + Cp–Ru), 6.77–7.27, 7.53, 7.91–7.97 (3 · m,
31H + 5H + 4H, Ph). 13C NMR: d 27.95–28.56 (m,
2 · CH2 of dppe), 31.42 [t, J(CP) 21.6 Hz, CH2 of dppm],
63.48, 67.63, 69.71 (2 · s, C5H4), 69.30 (s, Cp–Fe), 77.21,
83.25 (Cp–Ru), 91.02, 91.74 [t, J(CP) 2.6 Hz], 96.25,
125.99 [t, J(CP) 24.8 Hz, Ca], 127.80–128.13, 128.64,
128.97, 129.46–129.52, 130.98–131.14, 131.41–131.55,
132.71–132.91, 136.11–136.79, 141.62–142.13 (8 · m, Ph),
134.37 [t, J(CP) 15.9 Hz], 138.60 [t, J(CP) 23.6 Hz],
202.22 (CO), 206.68 (CO). 31P NMR: d 9.5 (dppm), 85.5
(dppe). ES-MS (MeOH, positive ion, m/z): 1436, M+.
For 4: Anal. Calc. for C53H38FeN4P2Ru: C, 67.02; H,
4.03; N, 5.90. Found: C, 66.94; H, 3.97; N, 6.02%. M,
950. IR (nujol): m(C„N) 2208m; m(C„C) 2163s, 1978vs;

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M.I. Bruce et al. / Journal of Organometallic Chemistry 692 (2007) 2564–2574
1
(d) With Os3(CO)10(NCMe)2.
A
mixture of
2015m, 1992w, 1990w (sh), 1815 vw (br) cmꢀ1. H NMR
(C6D6): d 2.14–2.28, 2.61–2.73 (2 · m, 2 · 2H, CH2), 3.72
(dd, J 2.4, 2.4 Hz, 1H, C5H3), 3.78 (s, 5H, Cp–Fe), 4.16
(dd, J 2.4, 1.2 Hz, 1H, C5H3), 4.26 (dd, J 2.4, 1.2 Hz,
C5H3), 4.72 (s, 5H, Cp–Ru), 6.29 (s, 1H), 6.93–6.96,
7.12–7.36, 7.96–8.01 (3 · m, 4H + 12H + 4H, Ph). 13C
NMR: d 27.96–28.76 (m, CH2), 64.25, 66.75, 67.61
(3 · m, C5H3), 69.19 (Cp–Fe), 77.21, 82.88 [t, J(CP) 2.2,
Cp–Ru], 83.78, 101.51, 109.84, 127.88–128.06, 128.39,
128.78, 129.66–129.78, 130.89–131.13, 131.40, 132.38,
134.33–134.67, 136.20, 136.35, 136.86, 141.17, 142.56–
143.00 (5 · m, Ph), 179.39 (CO). 31P NMR: d 88.3 (d, J
4.6), 88.5 (d, J 4.6) (AB quartet) (dppe). ES-MS
(MeOH + NaOMe, m/z): 1645, M+.
Fc(C„C)3Ru(dppe)Cp (50 mg, 0.061 mmol) and Os3-
(CO)10(NCMe)2 (57 mg, 0.061 mmol) in dry thf (10 ml)
was stirred at r.t. for 1 h. After removal of solvent under
vacuum, the residue was purified by preparative TLC (ace-
tone/hexane 2/1) to give the major dark red band
(Rf = 0.63) containing Os3{l3-FcC2C„CC„C[Ru(dp-
pe)Cp]}(CO)10 (7) (25 mg, 25%) as a purple crystalline solid
(CH2Cl2/hexane). Anal. Calc. for C57H38FeO10Os3P2Ru:
C, 40.94; H, 2.29. Found: C, 40.97; H, 2.32%. M, 1673.
IR (CH2Cl2): m(CC) 2128w (br); m(CO) 2092m, 2062vs,
2050s, 2019m, 2000m, 1821w (br) cmꢀ1
.
1H NMR
(C6D6): d 1.90–2.10, 2.40–2.60 (2 · m, 2 · 2H, CH2), 4.00,
4.27 (2 · m, 2 · 2H, C5H4), 4.23 (s, 5H, Cp–Fe), 4.60 (s,
5H, Cp–Ru), 6.94, 7.12–7.16, 7.22–7.27, 7.31–7.36, 7.85–
7.90 (5 · m, 6H + 4H + 2H + 4H + 4H, Ph). 13C NMR
(C6D6): d 28.04–28.96 (m, CH2), 53.66, 70.41, 70.77
[2 · m (br), C5H4], 70.51 (Cp–Fe), 83.95 (Cp–Ru), 90.18,
95.54, 99.09, 104.23, 129.23, 129.52, 132.18–132.32,
134.33–134.47, 135.06–135.29, 136.97–137.65, 142.19–
142.83 (7 · m, Ph), 152.91, 179.16 (br, CO). 31P NMR
(C6D6): d 85.6 (dppe). ES-MS (MeOH + NaOMe, negative
ion, m/z): 1704, [M+OMe]ꢀ.
Isomerisation of 7. A sample of Os3{l3-FcC2C„
CC„C[Ru(dppe)Cp]}(CO)10 (45 mg, 0.027 mmol) was dis-
solved in CDCl3 (3 ml) and stirred for 2 d at r.t. After
removal of solvent, the residue was purified by preparative
TLC (hexane/acetone 2/1) to give a major brown fraction,
tentatively identified as Os3(l–H){l3-CpFe(g-C5H3)CCH
4.7. Structure determinations
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
˚
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 [36]. Pertinent results are given
in the Figures (which show non-hydrogen atoms with 50%
probability amplitude displacement envelopes and hydro-
C„CC„C[Ru(dppe)Cp]}(CO)8
(8)
(27 mg,
60%),
obtained as a brown crystalline solid. Anal. Calc. for
C56H38FeO9Os3P2Ru: C, 40.94; H, 2.29. Found: C, 39.97;
H, 1.82%. M, 1645. IR (CH2Cl2): m(CO) 2092w, 2054vs,
˚
gen atoms with arbitrary radii of 0.1 A) and in Tables 1
Table 2
Crystal data and refinement details
Complex
2
4
6a
7
Formula
C47H38FeP2Ru. C6H6
899.80
Monoclinic
P21/n
9.964(2)
15.347(3)
C53H38FeN4P2Ru.CH2Cl2
1034.74
Monoclinic
P21/c
11.073(4)
22.688(8)
C76H60Co2FeO4P4Ru
1435.99
Monoclinic
P21/n
18.240(3)
17.820(1)
C57H38FeO10Os3P2Ru.CH2Cl2
1757.34
Triclinic
Molecular weight
Crystal system
Space group
ꢀ
P1
˚
a (A)
9.282(4)
16.710(7)
19.255(8)
74.878(10)
89.834(10)
74.479(10)
2771
˚
b (A)
˚
c (A)
27.876(4)
17.649(6)
21.315(2)
a (ꢁ)
b (ꢁ)
c (ꢁ)
96.643(3)
94.581(7)
107.333(6)
3
˚
V (A )
4234
4420
6614
Z
4
4
4
2
qcalc (Mg mꢀ3
2hmax (ꢁ)
)
1.412
53
0.81
0.79
1.555
50
0.91
0.78
1.442
42
0.37
0.82
2.106
65
7.6
0.57
l(Mo Ka) (mmꢀ1
Tmin/max
)
Crystal dimensions (mm)
Ntotal
0.35 · 0.24 · 0.18
16511
7503 (0.047)
5710
0.12 · 0.10 · 0.04
32944
7758 (0.17)
5031
0.11 · 0.04 · 0.02
185506
22806 (0.079)
15044
0.32 · 0.10 · 0.08
42819
20215 (0.046)
13867
N (Rint
Ntotal
R
)
0.045
0.096
0.075
0.058
Rw
0.055
0.196
0.140
0.094
a
˚
Data were measured using synchrotron radiation, k = 0.48595 A.

M.I. Bruce et al. / Journal of Organometallic Chemistry 692 (2007) 2564–2574
2573
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two sets of sites, occupancies refining to 0.703(8) and
complement.
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Acknowledgements
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[7] (a) N. Le Narvor, L. Toupet, C. Lapinte, J. Am. Chem. Soc. 117
(1995) 7129;
We thank Professor Brian Nicholson (University of
Waikato, Hamilton, New Zealand) for providing the mass
spectra, the ARC for support of this work and Johnson
Matthey plc, Reading, for a generous loan of RuCl3 Æ
nH2O. Use of the ChemMatCARS Sector 15 at the Ad-
vanced Photon Source was supported by the Australian
Synchrotron Research Program, which is funded by the
Commonwealth of Australia under the Major National
Research Facilities Program. ChemMatCARS Sector 15
is also supported by the National Science Foundation/
Department of Energy under Grant Nos. CHE9522232
and CHE0087817 and by the Illinois Board of Higher Edu-
cation. The Advanced Photon Source is supported by the
US Department of Energy, Basic Energy Sciences, Office
of Science, under Contract No. W-31-109-Eng-38.
(b) F. Coat, M.-A. Guillevic, L. Toupet, F. Paul, C. Lapinte,
Organometallics 16 (1997) 5988;
(c) M. Guillemot, L. Toupet, C. Lapinte, Organometallics 17 (1998)
1929;
(d) F. Coat, F. Paul, C. Lapinte, L. Toupet, K. Costuas, J.-F. Halet,
J. Organomet. Chem. 683 (2003) 368.
[8] (a) M.I. Bruce, P.J. Low, K. Costuas, J.-F. Halet, S.P. Best, G.A.
Heath, J. Am. Chem. Soc. 122 (2000) 1949;
(b) M.I. Bruce, B.D. Kelly, B.W. Skelton, A.H. White, J. Organomet.
Chem. 604 (2000) 150;
(c) M.I. Bruce, B.G. Ellis, P.J. Low, B.W. Skelton, A.H. White,
Organometallics 22 (2003) 3184.
[9] (a) T. Ren, G. Zou, J.C. Alvarez, Chem. Commun. (2000) 1197;
(b) T. Ren, G.-L. Xu, Comments Inorg. Chem. 23 (2002) 355;
(c) G.L. Xu, G. Zou, Y.-H. Ni, M.C. DeRosa, R.J. Crutchley, T.
Ren, J. Am. Chem. Soc. 125 (2003) 10057;
(d) T. Ren, Organometallics 24 (2005) 4854;
(e) G.-L. Xu, R.J. Crutchley, M.C. DeRosa, Q.-J. Pan, H.-X. Zhang,
X. Wang, T. Ren, J. Am. Chem. Soc. 127 (2005) 13354.
Appendix A. Supplementary material
[10] (a) T. Rappert, O. Nurnberg, H. Werner, Organometallics 12 (1993)
¨
Full details of the structure determinations (except
structure factors) have been deposited with the Cambridge
Crystallographic Data Centre. CCDC 620037, 620038,
620039 and 620040 contain the supplementary crystallo-
graphic data for this paper. These data can be obtained free
of charge via http://www.ccdc.cam.ac.uk/conts/retriev-
ing.html, or from the Cambridge Crystallographic Data
Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax:
(+44) 1223-336-033; or e-mail: deposit@ccdc.cam.ac.uk.
Supplementary data associated with this article can be
found, in the online version, at doi:10.1016/j.jorganchem.
2007.02.043.
1359;
(b) H. Werner, R.W. Lass, O. Gebert, J. Wolf, Organometallics 16
(1997) 4077;
(c) J. Gil-Rubio, M. Laubender, H. Werner, Organometallics 17
(1998) 1202;
(d) J. Gil-Rubio, B. Weberndo¨rfer, H. Werner, Angew. Chem., Int.
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(e) J. Gil-Rubio, M. Laubender, H. Werner, Organometallics 19
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(b) J. Stahl, J.C. Bohling, E.B. Bauer, T.B. Peters, W. Mohr, J.M.
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