Trimetallic complexes containing 1,1′-Rc′(C{triple bond, long}C)2 units [Rc′ = ruthenocene-1,1′-diyl, Ru(η-C5H4-)2]

Article abstract of DOI:10.1016/j.jorganchem.2006.11.037

Reactions between 1,1′-(Me₃SiC{triple bond, long}C)₂Rc′ [Rc′ = ruthenocen-1,1′-diyl, Ru(η-C₅H₄-)₂] and RuCl(PP)Cp′ in the presence of KF gave 1,1′-{Cp(PP)RuC{triple bond, long}C}₂Rc′ [Cp′ = Cp, PP = PPh₃ 1, P(m-tol)₃ 2, dppe 3, dppf 4; Cp′ = Cp^*, PP = dppe 5]. Compounds 1 and 2 react with tcne to give two diastereomers a/b of the allylic (vinylcarbene) complexes 6 and 7, while methylation of 5 gave the bis-vinylidene [1,1′-{Cp^*(dppe)Ru{double bond, long}C{double bond, long}CMe}₂Rc′](BPh₄)₂ (8). The X-ray structures of 4, 6b and 8 have been determined. Cyclic voltammograms indicate that there is some electronic communication between the ruthenium end-groups through the Rc′ centre.

Full text of DOI:10.1016/j.jorganchem.2006.11.037

Journal of Organometallic Chemistry 692 (2007) 1757–1765
www.elsevier.com/locate/jorganchem
Trimetallic complexes containing 1,10-Rc0(C„C)2
units [Rc0 = ruthenocene-1,10-diyl, Ru(g-C5H4–)2]
a,
a
a
b
b
Michael I. Bruce *, Martyn Jevric , Gary J. Perkins , 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 19 October 2006; received in revised form 23 November 2006; accepted 23 November 2006
Available online 1 December 2006
Abstract
Reactions between 1,10-(Me3SiC„C)2Rc0 [Rc0 = ruthenocen-1,10-diyl, Ru(g-C5H4–)2] and RuCl(PP)Cp0 in the presence of KF gave
1,10-{Cp(PP)RuC„C}2Rc0 [Cp0 = Cp, PP = PPh3 1, P(m-tol)3 2, dppe 3, dppf 4; Cp0 = Cp*, PP = dppe 5]. Compounds 1 and 2 react
with tcne to give two diastereomers a/b of the allylic (vinylcarbene) complexes 6 and 7, while methylation of 5 gave the bis-vinylidene
[1,10-{Cp*(dppe)Ru@C@CMe}2Rc0](BPh4)2 (8). The X-ray structures of 4, 6b and 8 have been determined. Cyclic voltammograms indi-
cate that there is some electronic communication between the ruthenium end-groups through the Rc0 centre.
ꢀ 2006 Elsevier B.V. All rights reserved.
Keywords: Ethynyl complexes; Ruthenocene; Ruthenium–phosphine; X-ray structure; tcne Cycloaddition
1. Introduction
trans-Pt2(l-dppm)2(C„CFc)2, [Cu3(l-dppm)3(l3-C„CFc)2]+
[9] and trans-Ru2(l-Y-dmba)4{(C„C)mFc}{(C„C)nFc}
[Y-dmba = (MeN)2C6H4Y, Y = H, OMe; m, n = 1, 2] [10]
have also been studied. In most of these, medium to strong
electronic coupling between the two Fc nuclei has been
noted.
Complexes containing redox-active transition metal
end-groups linked by carbon chains have attracted much
attention because of their possible use as models for molec-
ular wires [1,2]. End-capping of the carbon chain with
ferrocenyl groups has also been investigated, an early study
being of the complexes Fc(C„C)nW(CO)3Cp (n = 1–4) in
which lengthening the carbon chain results in an increase
in the oxidation potential of the ferrocene centre [3]. A
combination of the decreased electron donor ability of
the longer carbon chains and an increase in electron trans-
fer from the ferrocene group to the chain was considered to
be responsible for these features.
Several reports describing the syntheses and redox
activity of bis(ferrocenylethynyl)metal derivatives have also
appeared, the first examples of which were trans-
Pt(C„CFc)2(PR3)2 [4] and trans-Ru(C„CFc)2(dppx)2
(x = m [5–7], e [8]). Some polynuclear complexes, including
When the carbon chains are end-capped with a redox-
active group, such as Ru(PP)Cp0 [PP = (PPh3)2, dppe,
dppf; Cp0 = Cp, Cp*], and a metallocene centre (Mc = Fc,
Rc), electrochemical and spectroscopic studies of the
complexes McC„CRu(PP)Cp0 found there to be a consid-
erable interaction between the two end-caps, mediated by
the carbon chain [11,12]. The radical cation obtained by
one-electron oxidation has some delocalised character.
More recently, we described some complexes in which
two metal-ethynyl substituents are bridged by the ferro-
cene-1,10-diyl group and extensive electrochemical and
spectroscopic (IR, UV–Vis-near IR, Mo¨ssbauer) measure-
ments supported the conclusion that the ferrocene-1,10-diyl
moiety acts as an insulator when inserted into the C4 chain
[12]. This contrasts with the situation found for
{Ru(PP)Cp0}2(l-C„CC„C) [13].
*
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.2006.11.037

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M.I. Bruce et al. / Journal of Organometallic Chemistry 692 (2007) 1757–1765
In the case of ruthenocene complexes, Sato and cowork-
previously from HC„CRc and RuCl(PPh3)2Cp [14] and
the identity of the present product was confirmed by com-
parison with the reported material. These compounds were
characterised by an elemental microanalyses and by limited
spectroscopic studies. Their IR spectra contained m(C„C)
absorptions between 2074 and 2110 cmꢀ1 and the 1H
NMR spectra contained singlet resonances for the RuCp
groups between d 4.36 and 4.58, or at d 1.65 for the Cp*
Me resonance in 4. The C5H4 protons gave rise to two
unresolved multiplets between d 4.09 and 4.54, and 4.38
and 5.12; in 5, the overlap of the Fe– and Ru–C5H4 signals
gave four multiplets between d 3.77 and 5.93. Electrospray
mass spectra (ES MS) contained M+ or [M + Na]+ ions,
together with [Ru(PP)Cp0]+ in some cases, as detailed in
Section 4. The overall geometry of these complexes was
confirmed with the single-crystal X-ray structural determi-
nation of 4 (see below).
ers [14] have found two reversible one-electron oxidation
waves for complexes RcC„CRu(PP)Cp0 [PP = (PPh3)2,
dppe; Cp = Cp, Cp*] and that the second oxidation is
followed by unusual structural rearrangements leading to
vinylidene or allenylidene cations. In the case of Rc#C„
CRu(PPh3)2Cp [Rc# = Cp*Ru(g-C5H4–)], the vinylidene
cation [Rc#CH@C@Ru(PPh3)2Cp]+ was formed after
removal of one electron (the source of the proton was
not identified). Similarly, complexes containing Cp0Ru-
(g-C5H4C„C–) (Cp0 = Cp, Cp*) and CpRu(g-C5Me4C„
C–) ligands have been found to undergo two oxidation
processes followed by a structural rearrangement [15]. It
was therefore of interest to investigate derivatives with
ruthenocene-1,10-diyl groups bridging two redox-active
end-groups. This paper describes the syntheses and some
properties of compounds of this type.
The reactions of 1 and 2 with the electron-deficient
alkene C2(CN)4 (tcne) afforded orange bis-adducts, which
were characterised as the dienyls 6 (42%) and 7 (44%)
(Scheme 2).
As found for the analogous ferrocene complexes [12],
these were obtained as mixtures of diastereomers (63/37
for 6a/b, 36/64 for 7a/b), which could be converted to the
2. Results and discussion
Several complexes containing various –C„CRu(PP)Cp0
[PP = (PPh3)2, dppm, dppe, dppf; Cp = Cp, Cp*] groups
attached to a ruthenocene-1,10-diyl bridge were made by
the metalla-desilylation reaction described earlier [16]
(Scheme 1).
Thus, reactions of 1,10-(Me3SiC„C)2Rc with
RuCl(PP)Cp0 gave 1,10-{Cp(Ph3P)2RuC„C}2Rc0 (1;
86%), 1,10-{Cp([m-tol]3P)2RuC„C}2Rc0 (2; 86%), 1,10-
{Cp(dppe)RuC„C}2Rc0 (3; 39%), 1,10-{Cp*(dppe)2Ru-
C„C}2Rc0 (4; 47%), and 1,10-{Cp(dppf)RuC„C}2Rc0 (5;
75%), as yellow solids. The PPh3 complex has been made
C
C
Ru
PR3
R3P
PR3
Ru
Ru
R3P
C
C
Me3Si
R5
C
C
(NC)2C
C(CN)2
- PR3
Ru
+
Ru
Cl
P
P
C
(CN)2
C
C
a
SiMe3
C(CN)2
C
R3P
KF / MeOH
Ru
C
C
Ru
C
Ru
PR3
C
R5
C(CN)2
(CN)2
C(CN)2
Ru
b
C
P
C
P
C
C(CN)2
C
Ru
R3P
C
P
Ru
Ru
P
(NC)2C
Ru
C
Ph
C
M
C
R5
C
(CN)2
R = H, PP = (PPh3)2 1; {P(m-tol)3}2 2; dppe 3; dppf 4
R = Me, PP = dppe 5
R = Ph 6,
m-tol 7
Scheme 1.
Scheme 2.

M.I. Bruce et al. / Journal of Organometallic Chemistry 692 (2007) 1757–1765
1759
R5
assigned similarly. The molecular structure of 6b has been
determined and is described below.
Methylation of 4 with MeI in the presence of Na[BPh4]
resulted in formation of the bis-vinylidene complex [1,10-
{Cp*(dppe)Ru@C@CMe}2Rc0](BPh4)2 (8) as a pink solid
in 89% yield (Scheme 3).
Ru
C
P
C
P
Ru
This complex is characterised by 1H NMR resonances at
d 1.52 (Cp* and Me, overlapping) and 3.63, 4.08 (C5H4), as
well as the usual dppe CH2 and Ph signals, and in the 13C
NMR spectrum by resonances at d 10.12 and 102.49 (Cp*
Me and ring C), 12.06 (Me), and the downfield Ca triplet
at d 347.08 [J(CP) 16.7 Hz]. Other resonances from the
Rc0 moiety are assigned in Section 4.
P
P
C
C
Ru
R5
MeI
[NH4]PF6
R5
2.1. Molecular structures
2+
Me
Plots of single molecules of 4, 6b and the cation in 8
(which is isomorphous with the ferrocene analogue
described earlier [12]) are shown in Figs. 1–3, with selected
bond parameters collected in Table 1.
C
C
Ru
P
P
Ru
P
P
Ru
C
C
In 4, molecule 2 of 6b, and 8, the molecule is disposed
about a crystallographic inversion centre; in 6b, there is a
further molecule, devoid of crystallographic symmetry.
The structures are similar to their ferrocene analogues
and geometrical differences are limited to the expected dif-
ferences which result from replacing Fe by Ru in the metal-
locene. Thus the Ru(PP)Cp0 moieties have the usual
pseudo-octahedral geometries [Ru–P, 2.268, 2.277(1) 4;
2.376, 2.387(2) 6b; 2.300, 2.317(1) 8; Ru–C(cp), (av.)
2.26(2) 4, 2.22(1) 6b, 2.29(2) (Cp*) 8 ; Ru–C(1), 2.019(5)
R5
Me
R = Me, PP = dppe (8)
Scheme 3.
single isomers b by heating in refluxing benzene overnight.
The 13C NMR spectrum of 6b (major isomer) contained
resonances at d 6.74, 64.65, 67.94, 74.96, 75.03, 77.33 (four
singlets for the Ru–C5H4 groups), 85.04, 85.98, 91.85 (Ru–
Cp), 110.85, 115.59, 119.29, 119.49 (four CN singlets), the
phenyl multiplets between d 128 and 134, and a downfield
signal at d 215.59 (Ru–Ca). These resonances are similar to
those found for the ferrocene analogue and have been
˚
4, 1.862(5) 8 A] with C(1)–C0(2) 1.220(7) in 4 and 1.322(7)
˚
A in 8. In the bridging Rc group, the Ru–C distances
˚
(Ææ) range between 2.17(1) and 2.20(2) A, which may be
compared with those in the ferrocene analogues
˚
[2.03–2.05 A] and reflect the difference in atomic radii
˚
between the two metals [Fe = 1.26, Ru = 1.34 A] [17].
Interestingly, the average Ru–C(Cp0) distances in the
122
111
1021
P(1)
121
102
205
201
204
112
212
1011
1031
Ru(2)
203
Ru(1)
2
1
104
202
105
P(2)
211
1051
222
1041
221
Fig. 1. Projection of an individual molecule of 1,10-{Cp*(dppe)RuC„C}2Rc0 4.

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M.I. Bruce et al. / Journal of Organometallic Chemistry 692 (2007) 1757–1765
CN(3402)
CN(1101)
302
301
205’
203
CN(1102)
204’
203’
11
205
34
102
112
321
Ru(2)
12
Ru(3)
CN(3401)
P(3)
33
13
202’
311
111
132
Ru(1)
121
32
31
201
P(1)
105
14
103
131
202
331
332
CN(1401)
CN(3101)
CN(3102)
CN(1402)
CN(4402)
422
CN(4401)
421
44
401
403
505
501
412
P(4)
411
43
42
Ru(5)
502
503
432
404
431
41
CN(4101)
CN(4102)
Fig. 2. Projections of the two molecules (the second centrosymmetric) of 1,10-{Cp(dppe)Ru[g3-C(CN)2CC@C(CN)2]}2Rc0 6b.
122
121
1011
111
1021
102
P(1)
10
3
112
Ru(1)
2
1031
1
105
201
20
212
P(2)
221
Ru(2)
204
211
202
1041
222
203
Fig. 3. Projection of the cation of [1,10-{Cp*(dppe)Ru@C@CMe}2Rc0](BPh4)2 8.

M.I. Bruce et al. / Journal of Organometallic Chemistry 692 (2007) 1757–1765
1761
Table 1
˚
Selected bond distances (A) and angles (ꢁ)
Complex
4
6b
8
˚
Bond distances (A)
Ru(1)–P(1)
2.277(1)
2.376(2), 2.387(1)
2.387(1)
2.317(1)
2.300(1)
Ru(1)–P(2)
2.268(1)
Ru(1)–C(cp)
2.242–2.278(4)
2.189–2.249(6),
2.197–2.248(5),
2.190–2.274(6)
2.21(3), 2.22(2),
2.22(3)
2.265–2.315(5)
(av.)
2.26(2)
2.29(2)
Ru(1)–C(1)
Ru(1)–C(2)
Ru(1)–C(3)
C(1)–C(2)
C(2)–C(3)
C(3)–C(4)
C(2)–C(201)
Ru(2)–C(cp)
2.019(5)
1.988(5), 1.975(4),
1.981(5) [C(n2)]
2.130(5), 2.123(5),
2.117(5) [C(n3)]
2.210(5), 2.179(4),
2.174(5) [C(n4)]
1.348(7), 1.353(7),
1.351(7)
1.439(7), 1.416(7),
1.431(7)
1.492(9), 1.480(7),
1.469(7)
1.463(9), 1.478(7),
1.467(7)a
2.149–2.196(5),
2.159–2.209(5)b
2.169(14), 2.18(2)
1.862(5)
1.220(7)
1.322(7)
1.522(9)
1.438(7)
1.472(8)
2.182–2.219(6)
2.195(15)
2.161–2.190(6)
2.175(11)
(av.)
Bond angles (ꢁ)
P(1)–Ru(1)–P(2)
P(1)–Ru(1)–C(1)
P(1)–Ru(1)–C(n2)
83.17(4)
84.8(1)
82.15(4)
93.0(2)
91.2(2), 90.6(2),
92.6(2)c
P(1)–Ru(1)–C(n3)
P(1)–Ru(1)–C(n4)
116.2(2), 114.8(1),
117.7(1)c
97.0(2), 96.0(1),
97.7(1)c
P(2)–Ru(1)–C(1)
Ru(1)–C(1)–C(2)
Ru(1)–C(n2)–C(n1)
83.9(1)
175.3(4)
82.2(2)
176.9(4)
147.3(4), 145.5(4),
147.4(4)
Ru(1)–C(n2)–C(n3)
Ru(1)–C(n3)–C(n01)
Ru(1)–C(n4)–C(n3)
75.0(3), 75.5(3),
74.8(3)
122.5(4), 129.1(4),
127.7(3)d
67.0(3), 67.9(3),
67.9(3)
C(1)–C(2)–C(201)
C(3)–C(2)–C(201)
C(n1)–C(n2)–C(n3)
178.1(4)
123.7(5)
117.2(5)
119.0(5)
[C(1)–C(2)–C(3)]
137.5(4), 138.1(5),
137.3(5)
C(n2)–C(n3)–C(n01)
C(n4)–C(n3)–C(n01)
121.8(4), 121.8(4),
123.9(4)
125.4(5), 126.1(4),
124.9(4)
˚
For 6b, C(14)–C(1401, 1302), C(31)–C(3101, 3102), C(41)–C(4101, 4102) are 1.41(1), 1.46(1); 1.445(8), 1.426(7); 1.439(8), 1.422(9) A.
a
Values for C(13)–C(201), C(33)–C(2030), C(43)–C(501).
Values for Ru(2), Ru(5).
Values for n = 1, 3, 4.
Values for Ru(1)–C(13)–C(201), Ru(3)–C(33)–C(2030), Ru(4)–C(43)–C(501).
b
c
d
substituents are longer than those in the Rc0 groups, prob-
ably because of increased steric hindrance caused by the
phosphine ligands.
In 4 and 8, the linear Ru–C(1)–C(2) moieties [angles
at C(1,2) 175.3, 178.1(4)ꢁ] are bridged by the Rc0 group
and are necessarily at 180ꢁ to one another. In 6b, the two

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M.I. Bruce et al. / Journal of Organometallic Chemistry 692 (2007) 1757–1765
Table 2
Electrochemical data
Complex [M]
E1
E2
DE1/2
KC(0/+1/+2)
E3
E4
Ru(PPh3)2Cp
Ru(dppe)Cp
Ru(dppe)Cp*
Ru[P(m-tol)3]2Cp
Ru(dppf)Cp
+0.18
+0.16
+0.02
+0.12
+0.27
+0.44
+0.30
+0.27
+0.36
+0.52
0.26
0.14
0.25
0.24
0.25
2.5 · 104
2.3 · 102
1.7 · 104
1.1 · 104
1.7 · 104
+0.61
+0.66
+0.59
+0.69
+0.77b
+0.75
+1.21a
+1.16a
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
Peak potential of a fully non-reversible wave.
Peak potential of a quasi-reversible wave.
b
substituents in molecule 1 form an angle of ꢀ155.8ꢁ about
essentially no electronic communication between the end-
groups. Conventional reactions with tcne and with MeI
gave the corresponding tetracyanobutadienyl and vinyli-
dene complexes, respectively.
the C(0)–Ru–C(00) axis.
2.2. Electrochemistry
We have studied the electrochemistry of these complexes
briefly, but as found for the analogous ferrocene deriva-
tives, there is little evidence for electronic communication
between the electron-rich Ru(PP)Cp0 groups through the
ruthenocene nucleus, insofar as no resolution of the oxida-
tion waves of these groups was found. Generally, the pre-
vious study by Sato and coworkers showed the presence
of irreversible 2ꢀe processes, although reversible 1ꢀe pro-
cesses were found if Na[B{C6H3(CF3)2-3,5}4] was used as
supporting electrolyte [14]. Potentials for related mononu-
clear complexes were determined as follows: Ru(C„
CPh)(PPh3)2Cp, +0.05; Ru(C„CPh)(PPh3)2Cp*, ꢀ0.26
(both 1ꢀe); RcC„CH, +0.58 V (2ꢀe, irrev.).
4. Experimental
4.1. General
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
In the present study (Table 2), the expected increased
in ease of oxidation is found as the ligands associated
with the Ru–PR3 centre change in order of increasing
electron donor power: dppf < PPh3 < dppe < P(m-tol)3,
and when Cp is changed for Cp* (E1 + 0.16 and
+0.02 V, respectively). All complexes show three oxida-
tion steps, while the PPh3 and dppe complexes show four
oxidation steps. It is likely that two of these steps are
associated with the ruthenocene centre and, interestingly,
all processes involve only one electron, in contrast to the
2ꢀe oxidation found for ruthenocene itself. It has not
been possible to disentangle the processes at the different
centres and, while comproportionation constants, KC,
can be calculated for the species involved in E1 and
E2, the small values (ca. 102–104) suggest that these are
somewhat localised on the Ru–PR3 and ruthenocene cen-
tres, respectively. In the case of the dppf complex, there
is no extra wave that might be associated with the dppf
ligand.
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
Varian 2000 instrument (1H at 300.13 MHz, 13C at
75.47 MHz, 31P at 121.503 MHz). Unless otherwise sta-
ted, samples were dissolved in CDCl3 contained in
5 mm sample tubes. Chemical shifts are given in ppm rel-
1
ative to internal tetramethylsilane for H and 13C NMR
spectra and external H3PO4 for 31P NMR spectra. Elec-
trospray mass spectra (ES MS) were obtained from sam-
ples dissolved in MeOH unless otherwise indicated.
Solutions were injected into a Varian Platform II spec-
trometer via a 10 ml injection loop. Nitrogen was used
as the drying and nebulising gas. Chemical aids to ioni-
sation were used [18].
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 and ferrocene as internal calibrant (FeCp2/
[FeCp2]+ = 0.46 V). The cell contained a Pt-mesh working
electrode, Pt wire counter and pseudo-reference electrodes.
Elemental analyses were by CMAS, Belmont, Vic.,
Australia.
3. Conclusions
Reactions between 1,10-(Me3SiC„C)2Rc0 and RuCl-
(PP)Cp0 in the presence of KF have given several com-
plexes containing redox-active Ru(PP)Cp0 centres bridged
by Rc0(C„C–)2 ligands. Electrochemical studies revealed
that, as with the analogous ferrocene derivatives, there is

M.I. Bruce et al. / Journal of Organometallic Chemistry 692 (2007) 1757–1765
1763
4.3. Reagents
MeOH (35 ml) pure 1,10-{Cp*(dppe)RuC„C}2Rc0
(4) (130 mg, 47%) was isolated as a yellow crystalline
solid. Anal. Calc. (C86H86P4Ru3): C, 66.78; H, 5.60;
M, 1547. Found: C, 66.70; H, 5.64%. IR (nujol,
cmꢀ1): m(C„C) 2099w, 2077s; other bands at
1585w, 1572w. 1H NMR (C6D6): d 1.65 (s, 30H,
Cp*), 1.80–2.00, 2.60–2.80 (2 · m, 2 · 4H, CH2 of
dppe), 4.48, 4.75 (2 · m, 2 · 4H, C5H4 of Rc0),
7.06–7.33, 7.92–8.01 (2 · m, 32 + 8H, Ph). 31P
NMR: d 80.8. ES MS (MeOH, m/z): 1547, M+;
914, [M + H ꢀ Ru(dppe)Cp*]+.
RuCl(PP)Cp0 (PP = (PPh3)2, Cp0 = Cp [19]; PP = dppe,
Cp0 = Cp* [20]) were obtained as previously described; tcne
(Aldrich) was sublimed before use.
4.3.1. Preparation of 1,10-(Me3SiC„C)2Rc0
This compound was made in 57% yield from 1,10-di-
acetylruthenocene by the same procedure as the ferrocene
analogue [21]. 1H NMR: d 0.16 (s, 18H, SiMe3), 4.53–
4.55, 4.79–4.81 (2 · m, 2 · 2H, C5H4).
(e) With RuCl(dppf)Cp.
A
degassed solution of
4.3.2. Reactions of 1,10-(Me3SiC„C)2Rc0
RuCl(dppf)Cp (143 mg, 0.176 mmol), 1,10-(Me3-
SiC„C)2Rc0 (41 mg, 0.095 mmol) and KF (22 mg,
0.38 mmol) in MeOH (35 ml) was heated at reflux
point for 24 h. After cooling to r.t., the resulting pre-
cipitate was collected and washed with MeOH and
hexane to give pure 1,10-{Cp(dppf)RuC„C}2Rc0 (5)
(113 mg, 75%) as a bright yellow solid. Anal. Calc.
(C92H74Fe2P4Ru3): C, 64.30; H, 4.34; M, 1718.
Found: C, 63.98; H, 4.42%. IR (nujol, cmꢀ1):
m(C„C) 2105w, 2084s; other bands at 1585w,
1571w. 1H NMR (C6D6): d 3.77, 4.29, 4.61, 5.93
(4 · m, 4 + 8 + 4 + 4 H, Ru–C5H4), 4.36 (s, 10H,
Ru–Cp), 5.23 (m, 4H, Fe–C5H4), 7.53, 8.18 (2 · m,
10 + 8H, Ph) The remaining 22 Ph protons are under
the C6H6 peak at d 7.16. 31P NMR: d 56.1. ES MS
(MeOH, m/z): 1718, M+.
(a) With RuCl(PPh3)2Cp. A degassed solution of RuCl-
(PPh3)2Cp (403 mg, 0.555 mmol), 1,10-(Me3SiC„C)2-
Rc0 (108 mg, 0.251 mmol) and KF (51 mg, 0.88
mmol) in MeOH/thf (30/10 ml) was heated at reflux
point for 16 h. After cooling to r.t., the resulting pre-
cipitate was collected and washed successively with
MeOH, Et2O and hexane to give pure 1,10-
{Cp(PPh3)2RuC„C}2Rc0 (1) (240 mg, 58%) as a yel-
low solid. Anal. Calc. (C96H78P4Ru3): C, 69.51; H,
4.74; M, 1658. Found: C, 69.62; H, 4.81%. IR (nujol,
cmꢀ1): m(C„C) 2074s; other bands at 1587w, 1572w.
1H NMR (C6D6): d 4.25, 5.00 (2 · m, 2 · 4H, C5H4 of
Rc0), 4.42 (s, 10H, Ru–Cp), 7.00, 7.73 (2 · m, 40 + 20
H, Ph). 31P NMR: d 52.2. ES MS (MeOH, m/z):
1658, M+; 690, [Ru(PPh3)2Cp]+.
(b) With RuCl{P(m-tol)3}2Cp. Similarly, from RuCl-
{P(m-tol)3}2Cp (171 mg, 0.232 mmol), 1,10-(Me3-
SiC„C)2Rc0 (49 mg, 0.116 mmol) and KF (12 mg,
0.207 mmol) and refluxing for 18 h, was obtained
1,10-{Cp[P(m-tol)3]2RuC„C}2Rc0 (2) (182 mg,
4.3.3. Reaction between 1,10-{Cp(PPh3)2RuC„C}2Rc0 and
tcne
Tetracyanoethene (17 mg, 0.13 mmol) was added to a
stirred suspension of 1,10-{Cp(PPh3)2RuC„C}2Rc0 (93
mg, 0.56 mmol) in dry CH2Cl2 (20 ml) and the mixture
was stirred for 2 d. Removal of solvent under vacuum
and purification of the residue by preparative t.l.c. (ace-
tone-CH2Cl2 1/99) afforded a mixture of diastereomers (63
a/37 b) of the bis-adduct 6 (33 mg, 42%) as an orange solid.
Conversion of 6b to 6a was achieved by heating a solution
in refluxing benzene overnight. Anal. Calc. (C72H48-
N8P2Ru3): C, 62.20; H, 3.48; N, 8.06; M, 1390. Found:
C, 62.21; H, 3.39; N, 8.09%. IR (nujol, cmꢀ1): m(CN)
2214s; other band at 1616m. ES MS (MeOH, m/z): 1413,
[M + Na]+. NMR data: Minor isomer 6a: 1H NMR: d
4.61 (s, 10H, Ru–Cp), 5.12, 5.16, 5.34, 6.01 (4 · m,
4 · 2H, C5H4), 7.35–7.53 (m, 30H, Ph). 13C NMR: d 7.00
(d, J 6.0 Hz), 64.59 (d, J 2.3 Hz), 70.32, 72.36, 75.36,
77.20 (4 · s, C5H4), 84.50 (d, J 8.3 Hz), 86.11, 91.85 (Ru–
Cp), 111.03 (d, J 2.5 Hz, CN), 115.56, 119.18, 119.39
(3 · s, CN), 128.47–128.62, 131.25, 134.20–134.34 (3 · m,
Ph), 216.47 (d, J 13.4 Hz). 31P NMR: d 40.5. Major isomer
6b: 1H NMR: d 4.59 (s, Ru–Cp), 5.17, 5.18, 5.27, 5.84
(4 · m, 4 · 2H, C5H4), 7.35–7.53 (m, 30H, Ph). 13C
NMR: d 6.74 (d, J 5.1 Hz), 64.65 (d, J 2.3 Hz), 67.94,
74.66, 75.03, 77.33 (4 · s, C5H4), 85.04 (d, J 8.3 Hz),
85.98, 91.85 (Ru–Cp), 110.85 (d, J 2.7 Hz), 115.59,
86%) as a yellow solid. Anal. Calc. (C108H102
-
P4Ru3): C, 71.00; H, 5.63; M, 1827. Found: C,
70.93; H, 5.61%. IR (nujol, cmꢀ1): m(C„C) 2081s;
1
other band at 1591w. H NMR (C6D6): d 2.05 (s,
36H, Me), 4.54, 5.12 (2 · m, 2 · 4H, C5H4 of Rc0),
4.58 (s, 10H, Ru–Cp), 6.84–7.71 (m, 48H, tol). 31P
NMR: d 51.8. ES MS (MeOH, m/z): 1827, M+.
(c) With RuCl(dppe)Cp. Similarly, from RuCl(dppe)Cp
(153 mg, 0.255 mmol), 1,10-(Me3SiC„C)2Rc0 (54
mg, 0.126 mmol) and KF (22 mg, 0.38 mmol) in
MeOH (35 ml), was obtained pure 1,10-{Cp(dppe)-
RuC„C}2Rc0 (3) (70 mg, 39%) as a yellow solid.
Anal. Calc. (C76H66P4Ru3): C, 64.90; H, 4.73; M,
1407. Found: C, 64.79; H, 4.62%. IR (nujol, cmꢀ1):
m(C„C) 2111m, 2093s; other bands at 1586w,
1572w. 1H NMR (C6D6): d 1.95–2.15, 2.55–2.75
(2 · m, 2 · 4H, CH2 of dppe), 4.09, 4.38 (2 · m, 2·
4H, C5H4 of Rc0), 6.96–6.97, 7.19–7.31, 7.99–8.04
(3 · m, 12 + 20 + 8H, Ph). 31P NMR: d 86.9. ES
MS (MeOH, m/z): 1430, [M + Na]+.
(d) With RuCl(dppe)Cp*. Similarly0, from RuCl(dp-
pe)Cp* (289 mg, 0.431 mmol), 1,1 -(Me3SiC„C)2Rc0
(77 mg, 0.18 mmol) and KF (27 mg, 0.47 mmol) in

1764
M.I. Bruce et al. / Journal of Organometallic Chemistry 692 (2007) 1757–1765
Table 3
Crystal data and refinement details
Complex
4
6b
8
Formula
MW
Crystal system
Space group
C86H86P4Ru3 Æ 2C4H8O
1691.05
Triclinic
C72H48N8P2Ru3 Æ 1.33CH2Cl2
1503.67
Triclinic
C88H92P4Ru23þ ꢁ 2C24H20Bꢀ
2215.39
Monoclinic
P21/n
16.243(2)
18.275(2)
18.655(2)
ꢀ
ꢀ
P1
P1
˚
a (A)
12.027(3)
12.106(3)
15.637(4)
72.100(4)
67.750(4)
89.977(4)
1987
12.102(1)
16.019(1)
24.952(2)
76.698(2)
89.976(2)
88.308(2)
4706
˚
b (A)
˚
c (A)
a (ꢁ)
b (ꢁ)
c (ꢁ)
100.115(2)
3
˚
V (A )
5451
1.349
qc(g cmꢀ3
)
1.413
1.592
Z
1
3
2
2hmax (ꢁ)
58
0.69
60
0.93
0.85
53
0.52
0.91
l(Mo Ka) (mmꢀ1
Tmin/max
)
Crystal dimensions (mm3)
Ntot
0.12 · 0.12 · 0.04
18152
0.24 · 0.08 · 0.07
72613
0.38 · 0.17 · 0.13
40785
N (Rint
No
)
9342 (0.038)
7424
26997 (0.043)
19904
11060 (0.098)
8019
R
0.067
0.060
0.054
Rw (nw)
0.14 (20)
0.12 (62)
0.12 (7.2)
119.29, 119.49 (3 · s, CN), 128.47–128.62, 131.25, 134.20–
134.34 (3 · m, Ph), 215.59 (d, J 13.4 Hz). 31P NMR: d 40.5.
10.12 (C5Me5), 12.06 (Me), 69.83, 70.30 (2 · s, Ru–C5H4),
77.21 (Rc0 ipso), 102.48, 115.46, 125.37–125.40, 127.12–
127.21, 128.43–128.50, 131.9–131.74, 132.56–133.18,
134.18–134.94, 136.20 (6 · m, Ph), 163.17–165.14 (m),
347.08 [t, J(CP) 16.7 Hz, Ca]. 31P NMR: d 74.7. ES MS
4.3.4. Reaction between 1,10-{Cp[P(m-tol)3]2 RuC„C}2
Rc0 and tcne
The reaction was carried out as for the PPh3 complex,
using 1,10-{Cp[P(m-tol)3]2RuC„C}2Rc0 (100 mg, 0.055
mmol) and tcne (17 mg, 0.137 mmol) to give 7 as a 36/64
mixture of diastereomers as an orange solid (36 mg,
44%). Anal. Calc. (C78H60N8P2Ru3): C, 65.23; H, 3.91;
N, 7.25; M, 1475. Found: C, 65.23; H, 3.98; N, 7.28%.
IR (nujol, cmꢀ1): m(CN) 2213s; other band at 1614m. ES
MS (MeOH + NaOMe, m/z): 1498, [M + Na]+. NMR
(MeOH, m/z): 789, M2+
.
4.3.6. 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
1
data: Minor isomer 7a: H NMR: d 2.44 (s, 36H, Me),
˚
4.63 (s, 10H, Ru–Cp), 5.23, 5.32, 5.92 (3 · m, 4 + 2 + 2H,
monochromatic Mo Ka radiation, k = 0.71073 A. Aniso-
C5H4), 7.18–7.41 (m, 48H, tol). 31P NMR: d 39.5. Major
tropic displacement parameter forms were refined for the
1
isomer 7b: H NMR: d 1.30 (s, 36H, Me), 4.65 (s, Ru–
non-hydrogen atoms, (x, y, z, Uiso)H being included, con-
Cp), 5.08, 5.23, 5.39, 6.09 (4 · m, 4 · 2H, C5H4), 7.18–
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 [22].
7.41 (m, 48H, tol). 31P NMR: d 39.4.
4.3.5. Methylation of 1,10-{Cp*(dppe)RuC„C}2Rc0
Iodomethane (10 drops, excess) was added to a solution
of 1,10-{Cp*(dppe)RuC„C}2Rc0 (56 mg, 0.036 mmol) and
Na[BPh4] (50 mg, 0.15 mmol) in thf (20 ml) and the mixture
was heated at reflux point for 16 h. After cooling, solvent
was removed under vacuum and the residue was purified
by column chromatography (acetone-CH2Cl2 1/4) to give
1,10-[{Cp*(dppe)RuCMe@C@}2Rc0](BPh4)2 (8) (71 mg,
89%) as a pink solid. Anal. Calc. (C136H132B2P4Ru3): C,
73.74; H, 6.01; M (cation), 1578. Found: C, 73.74; H,
Pertinent results are given in the figures (which show
non-hydrogen atoms with 50% probability amplitude dis-
placement ellipsoids and hydrogen atoms with arbitrary
˚
radii of 0.1 A) and in Tables 1 and 3.
4.4. Variata
4. Displacement parameters on the solvent molecules
were high, O being tentatively assigned from the refinement
behaviour.
1
6.09%. IR (nujol, cmꢀ1): 1648m, 1616w, 1580w. H NMR
(C6D6): d 1.52 (br s, 36H, Cp* + Me), 2.00–2.50, (br m,
8H, CH2 of dppe), 3.63, 4.08 (2 · m, 2 · 4H, C5H4 of Rc0),
6.72–6.93, 7.13–7.48 (2 · m, 32 + 48H, Ph). 13C NMR: d
6b. One of the chloroform molecules was modelled as
disordered over a pair of sites, occupancies refining to
0.650(8) and complement.

M.I. Bruce et al. / Journal of Organometallic Chemistry 692 (2007) 1757–1765
1765
[7] Y. Zhu, O. Clot, M.O. Wolf, G.P.A. Yap, J. Am. Chem. Soc. 120
(1998) 1812.
Acknowledgement
[8] C. LeBreton, D. Touchard, L.L. Pichorn, A. Daridor, L. Toupet,
P.H. Dixneuf, Inorg. Chim. Acta 272 (1998) 188.
[9] (a) J.H.K. Yip, J. Wu, K.-Y. Wong, K.-W. Yeung, J.J. Vittal,
Organometallics 21 (2002) 1612;
(b) J.H.K. Yip, J. Wu, K.-Y. Wong, K.P. Ho, C.S.-N. Pun, J.J.
Vittal, Organometallics 21 (2002) 5292.
[10] 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.
[11] (a) M. Sato, H. Shintate, Y. Kawata, M. Sekino, M. Katada, S.
Kawata, Organometallics 13 (1994) 1956;
We thank Prof. Brian Nicholson (University of
Waikato, Hamilton, New Zealand) for providing the mass
spectra and the ARC for support of this work and Johnson
Matthey plc, Reading, for a generous loan of RuCl3 Æ
nH2O.
Appendix A. Supplementary material
(b) M. Sato, Y. Hayashi, S. Kumakura, N. Shimizu, M. Katada, S.
Kawata, Organometallics 15 (1996) 721.
[12] M.I. Bruce, P.J. Low, F. Hartl, P.A. Humphrey, F. de Montigny, M.
Jevric, C. Lapinte, G.J. Perkins, R.L. Roberts, B.W. Skelton, A.H.
White, Organometallics 24 (2005) 5241.
[13] (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.G. Ellis, P.J. Low, B.W. Skelton, A.H. White,
Organometallics 22 (2003) 3184.
[14] M. Sato, Y. Kawata, H. Shintate, Y. Habata, S. Akabori, K.
Unoura, Organometallics 16 (1997) 1693.
CCDC 619541, 619542 and 619543 contain the supple-
mentary crystallographic data for the compounds 4, 6
and 8. This material can be obtained free of charge via
www.ccdc.cam.ac.uk/conts/retrieving.html (or from the
CCDC, 12 Union Road, Cambridge CB2 1EZ, UK; fax:
+44 1223 336033; e-mail: deposit@ccdc. cam.ac.uk).
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