Synthesis, structures and some reactions of Ru(C≡CC≡CFc) (PP)Cp (PP=dppm, dppe) and related compounds

Article abstract of DOI:10.1016/j.jorganchem.2004.05.028

The compounds Ru(C≡CC≡CFc)(PP)Cp [PP=dppe (1), dppm (2)], have been obtained from reactions between RuCl(PP)Cp and FcC≡CC≡CSiMe₃ in the presence of KF (1) or HC≡CC≡CFc and K[PF₆] (2), both with added dbu. The dppe complex reacts with Co₂(CO)₆ (L₂)[L₂=(CO)₂, dppm] to give 3, 4 in which the Co₂(CO)₄ (L₂) group is attached to the outer C≡C triple bond. The PPh 3 analogue of 3 (5) has also been characterised. In contrast, tetracyanoethene reacts to give two isomeric complexes 6 and 7, in which the cyano-olefin has added to either C≡C triple bond. The reaction of RuCl(dppe)Cp with HC≡CC≡CFc, carried out in a thf/NEt₃ mixture in the presence of Na[BPh₄], gave [Ru{C≡CC(NEt₃)- CHFc}(dppe)Cp]BPh₄ (8), probably formed by addition of the amine to an (unobserved) intermediate butatrienylidene [Ru(-C-C-C-CHFc)(dppe)Cp]⁺. The reaction of I₂ with 8 proceeds via an unusual migration of the alkynyl group to the Cp ring to give [RuI(dppe) {η-C₅H₄ C≡CC(NEt₃)-CHFc}]I₃ (9). Single-crystal X-ray structural determinations of 1, 2 and 4-9 are reported. Published by Elsevier B.V.

Full text of DOI:10.1016/j.jorganchem.2004.05.028

Journal of Organometallic Chemistry 689 (2004) 2860–2871
www.elsevier.com/locate/jorganchem
Synthesis, structures and some reactions of Ru(C„CC„CFc)(PP)Cp
PP=dppm, dppe) and related compounds
(
a,
Michael I. Bruce , Fr e´ d e´ ric de Montigny , Martyn Jevric , Claude Lapinte ,
a,b
a
b
*
c
Brian W. Skelton , Mark E. Smith , Allan H. White
a
c
a
Department of Chemistry, University of Adelaide, SA 5005, Australia
UMR CNRS 6509, Institut de Chimie de Rennes, Universit e´ de Rennes 1, Campus de Beaulieu, 35042 Rennes, France
b
c
Department of Chemistry, University of Western Australia, Crawley, WA 6009, Australia
Received 5 March 2004; accepted 21 May 2004
Available online 22 July 2004
Abstract
The compounds Ru(C„CC„CFc)(PP)Cp [PP=dppe (1), dppm (2)], have been obtained from reactions between RuCl(PP)Cp
and FcC„CC„CSiMe in the presence of KF (1) or HC„CC„CFc and K[PF ] (2), both with added dbu. The dppe complex
3
6
reacts with Co
2
(CO)
6
(L
2
) [L
2
=(CO)
2
, dppm] to give 3, 4 in which the Co
2
(CO)
4
(L
2
) group is attached to the outer C„C triple bond.
analogue of 3 (5) has also been characterised. In contrast, tetracyanoethene reacts to give two isomeric complexes 6 and 7,
The PPh
3
in which the cyano-olefin has added to either C„C triple bond. The reaction of RuCl(dppe)Cp with HC„CC„CFc, carried out in
a thf/NEt mixture in the presence of Na[BPh ], gave [Ru{C„CC(NEt )‚CHFc}(dppe)Cp]BPh (8), probably formed by addition
3
4
3
4
+
of the amine to an (unobserved) intermediate butatrienylidene [Ru(‚C‚C‚C‚CHFc)(dppe)Cp] . The reaction of I
2
with 8 pro-
(9). Single-
ceeds via an unusual migration of the alkynyl group to the Cp ring to give [RuI(dppe){g-C
5
H
4
C„CC(NEt
3
)‚CHFc}]I
3
crystal X-ray structural determinations of 1, 2 and 4–9 are reported.
2004 Published by Elsevier B.V.
ꢀ
Keywords: Ruthenium; Carbon chain; Albynyl molecular wires
1
. Introduction
own interests, and those of others, have been centred
on compounds containing C chains, with groups such
4
*
*
Contemporary interest in compounds containing car-
as Re(CO) (bpy) [3], Re(NO)(PPh )Cp [4], Fe(CO) Cp
3 3 2
bon chains linking redox-active transition metal centres
stems from their possible use in nanotechnology and mi-
cro-electronics, including non-linear optics [1]. Possible
uses as models for molecular-scale wires and the ease
of study of such systems have resulted in a large litera-
ture describing a variety of such complexes [2]. Our
[5], Fe(dppe)Cp* [6], Ru(PPh ) Cp [7] and trans-
PtR(PAr ) (R=tol, C F ; Ar=Ph, tol) [8] as end-caps.
3 2
3
2
6 5
Previous reports from this group have described com-
pounds containing various ML fragments linked to re-
n
dox-active ferrocenyl (Fc) groups by carbon chains, e.g.,
{Cp(OC) W}(C„C) Fc (n=1–4) [9], in which the oxi-
3
n
dation potential of the Fc nucleus increased by ca.
.06 V per C„C unit added to the chain. Related stud-
Abbreviations: dbu; 1,8-diazabicyclo[5.4.0]undec-7-ene; dppe; 1,2-
0
0
bis(diphenylphosphino)ethane; dppf; 1,1 -bis(diphenylphosphino)fer-
rocene; Fc; ferrocenyl.
ies with Fc(C„C) Fc (n=2, 4) and ruthenium [10] or os-
n
*
mium [11] cluster carbonyls have given a variety of novel
complexes, for which electrochemical studies have also
Corresponding author. Fax: +61-8-8303-4358.
E-mail address: michael.bruce@adelaide.edu.au (M.I. Bruce).
0
022-328X/$ - see front matter ꢀ 2004 Published by Elsevier B.V.
doi:10.1016/j.jorganchem.2004.05.028

M.I. Bruce et al. / Journal of Organometallic Chemistry 689 (2004) 2860–2871
2861
been reported. Early papers by Sato and co-workers [12]
have reported that M(C„CFc)(L) Cp [M=Fe, Ru;
C401
2
C1
C2
C3
C4
Fe
Ru
L =(PPh ) , dppe, dppf] and some of the monocations
2
Ph2P
3 2
Fe
PPh2
(
CH2)n
C401
show interesting electron delocalisation properties. Fol-
C4
Ru
C1
C2 C3
(OC)2Co
lowing our earlier studies, the present venture has been
0
P
Co(CO)2
L
n = 2 (1), 1 (2)
P
to make derivatives containing both Fc and Ru(P) Cp
2
groups linked by C chains as described below.
4
L
PP
PP
=
=
dppe;
(PPh3)2, L
L
=
CO (3); LL = dppm (4)
= CO (5)
2
. Results and discussion
An attempt to make the PPh3 analogue of 1 af-
forded an orange solid which could not be purified sat-
isfactorily. However, derivatisation with Co (CO)
The metalla-desilylation of alkynyltrimethylsilanes
has proved to be a useful source of electron-rich alkynyl-
metals [13] and following this protocol, the reaction be-
2
8
afforded Ru{C„CC Fc[Co (CO) ]}(PPh ) Cp (5) as a
tween RuCl(dppe)Cp, FcC„CC„CSiMe and KF was
2
2
6
3 2
3
green crystalline solid, which exhibited three m(CC)
bands in its IR spectrum between 2077 and 2012
carried out in refluxing methanol containing dbu. Chro-
matographic work-up on basic alumina gave the desired
FcC„CC„CRu(dppe)Cp (1) in 57% yield as a yellow-
orange solid, based on recovered FcC„CC„CH (40%).
Characterisation was by spectroscopy [IR, NMR, elec-
trospray (ES) mass], together with a satisfactory elemen-
tal analysis (as for all compounds described below).
Finally, a single-crystal X-ray structure determination
provided confirmation of the identity of 1. In the IR
spectrum two m(CC) bands are found at 2174 and 2024
ꢀ
1
1
cm . In the H NMR spectrum, characteristic reso-
nances were found at d 4.26 (FeCp and RuCp, overlap-
ping) with other ferrocenyl protons at d 4.41 and 4.47
3
1
P
and aromatic protons between d 6.95 and 7.35. The
NMR spectrum contained a singlet at d 51.62. In the
ES-MS, a molecular ion at m/z 1210 fragmented to give
ions at m/z 883, 775 and 732, with the base peak at m/z
7
19. The structure of 5 was confirmed by an X-ray
study.
Of some interest was the reaction between 1 and
ꢀ
1
1
cm , while Cp resonances in the H NMR spectrum
are at d 4.03 and 4.65 (Fe, Ru, respectively) and at d
3
3
1
tetracyanoethene (tcne). When tcne was added to a so-
lution of 1 in thf, a deep green colouration appeared,
which rapidly changed to red-violet at r.t. The deep
green colour was longer lived at ꢀ78 ꢁC, suggesting
that the reaction proceeds via a radical intermediate.
The solution was heated to reflux point to complete
the reaction, after which a mixture of equal amounts
of two isomers of the tcne adduct of 1 were obtained
in a total yield of 67%. It proved difficult to separate
the two complexes by t.l.c., but fractional crystallisa-
tion afforded pure samples of each, although in low
yield. While the overall composition of each was as-
certained from the usual analytical and spectroscopic
measurements, the sites of addition were confirmed
by X-ray structure determinations; crystals of each
isomer were obtained by fractional crystallisation from
dichloromethane/cyclohexane mixtures. Further crys-
tallisation gave 6 as dark red crystals (from CH Cl /
.80 and 4.28 (C H of Fc). In the P NMR spectrum,
5 4
a singlet at d 85.97 is assigned to the dppe ligand. In the
ES-MS, the parent ion is found at m/z 798. The dppm
complex
2
was prepared from RuCl(dppm)Cp,
FcC„CC„CH, K[PF ] and dbu as an orange solid
6
(
28%). Its spectral properties are similar to those of 1,
1
ꢀ
including m(C„C) at 2174 and 2030 cm . In addition
to the resonances of the Cp, C H and dppm ligands,
the resonances of the C chain were observed at dC
5
4
4
6
9.96, 77.86, 96.31 and 114.95, the latter showing triplet
coupling (24.1 Hz) to the dppm P atoms and thereby as-
signed to the „C–Ru atom.
Cobalt carbonyl derivatives of 1 were obtained from
its reactions with either Co (CO) or Co (l-dppm)-
2
8
2
(
(
(
CO)6, which afforded Ru{C„CC Fc[Co (CO) ]}-
2
2
6
dppe)Cp (3) and Ru{C„CC Fc[Co (l-dppm)(CO) ]}-
2
2
4
dppe)Cp (4), respectively. The IR m(CO) spectra were
characteristic of the coordinated Co (CO) L groups,
between 2077 and 1976 (m-s-s-s-m pattern) and 2032–
2
2
2
6 2
hexane), while 7 formed red blocks (from acetone/hex-
ane). No evidence for the formation of a bis-adduct
was obtained when an excess of tcne was used in
the reaction.
ꢀ
1
935 (m-m-s-s-m) cm , respectively, the latter showing
1
the expected shift to lower energies when two CO groups
are replaced by the dppm ligand. Singlet resonances in
1
the H NMR spectra confirmed the retention of the
3
1
Cp groups attached to Fe and Ru, while the P NMR
C01(CN)2
C03(CN)2
C401
spectra contained resonances at d 87.22 (dppe in 3) or
C401
C4
Ru
C1
C1
C2
C3
Ru
3
6.30 and 86.35 (dppm, dppe in 4). Parent ions at m/z
084 and 1412, respectively, were found in the ES-MS.
Ph2P
2
Ph P
C2
C3
C4
(NC) C04
PPh2
1
In the case of 4, the structure was finally confirmed by
a single-crystal X-ray determination.
PPh2
NC)2C02
Fe
Fe
(
2
(6)
(7)

2862
M.I. Bruce et al. / Journal of Organometallic Chemistry 689 (2004) 2860–2871
The X-ray structural determinations described be-
low show that the tcne has added to the C„C triple
bond adjacent to the ruthenium centre in 6, while in
BPh4
I3
Fe
Fe
7
, addition has occurred to the triple bond next to
C401
C2
C201
C401
the ferrocenyl group. Of interest here is a comparison
of the atom separations in the cyanocarbon moieties.
˚
While the Ru–C(1) distance in 6 [2.046(3) A] is similar
to that expected for an unperturbed Ru–C (sp ) bond,
˚
that in 7 [1.915(4) A] is much shorter and is consistent
C4
C4
H
H
C1
C3
C1
C2
C3
Ru
Ph2P
3
N Et3
N3Et3
PPh2
Ph2P
2
Ru
PPh2
I
(
8)
(9)
with a significant contribution from the vinylidene
structure 7a. This is also supported by the relatively
˚
long C(1)–C(2) distance [1.230(3) A] and the equal
˚
C(2)–C(3) and C(3)–C(03) distances [1.377(3) A]. The
shorter C(4)–C(04) distance is comparable to both
C(1)–C(01) and C(2)–C(02) in 6.
During the initial attempts to characterise 8, addition
of iodine was found to give a brick-red solid, character-
ised as [RuI(dppe){g-C H C„CC(NEt )‚CHFc}]I
5
4
3
3
(
gration of the alkynyl group from ruthenium to the C5
9) by X-ray crystallography, in which an unusual mi-
C(CN)2
ring has occurred. The spectral properties of 9 include
31
ꢀ
1
[Ru]
C
m(CC) at 2197 and 1979 cm and the P resonance at
1 13
d 79.15 (dppe). In the H and C NMR spectra, the sin-
glet for the FeCp group were observed at dH 4.31 over-
laps both the ‚CH and one of the Fe(C H )
2.046 Å
C
C
C
Fc
(
NC)2C
5
4
(6)
resonances. The second resonance for the FeC H group
was found at d
5
4
N
C
N
4.52. The Ru(C H ) protons resonated
H 5 4
C
_
at d 5.09 and 5.50, these assignments being bases on
their higher chemical shifts. The C resonances for the
1
3
C
C
CN
Fc
C
C
CN
Fc
+
[Ru]
C
C
C
[Ru]
C
C
C
C5 rings were found at d 70.37 (FeCp), 71.24 and
72.02 (FeC
other resonances (see Section 4) are found between dC
7–120 and while not individually assigned, arise from
the carbons in the C chain and ipso carbons of the C
H ), and 78.43 and 88.13 (RuC H ). Several
4 5 4
5
1
.915 Å
(
NC)2C
2
(NC) C
7
(
7)
(7a)
4
5
rings. In the ES-MS, an ion with m/z 1026 corresponds
to the molecular cation.
3
The P NMR spectrum of a mixture of 6 and 7
1
contains two sets of signals which can be analysed
as an AB quartet [individual doublets at d 84.28 and
2.1. Molecular structures
8
5.43, J(PP) 16.8 Hz] and an AX system [doublet of
In the course of this work, single-crystal X-ray struc-
ture determinations were carried out to confirm the mo-
lecular structures. Plots of single molecules of 1, 2 and
4–7, and the cations of 8 and 9, are shown in Figs. 1
and 2 while Table 1 collects significant bond distances
and angles. Common features, such as the geometry
about the iron or ruthenium atoms, are in accord with
a myriad of related structures to be found in the Cam-
bridge Crystallographic Data Base [14]. Within the com-
doublets at d 66.06 and 82.34, J(PP) 21.4 Hz]. We as-
sign these resonances to 6 and 7, respectively, not only
because of the asymmetry inherent in the cyanocarbon
ligand, but also on the basis of restricted rotation
about the Ru–C(1) bond, both of which lead to the
observed inequivalence of the two P nuclei in each
complex.
Interesting transformations were found when the syn-
thesis of 1 from reactions of RuCl(dppe)Cp and
3
1
pounds reported here, average Fe–C(cp) distances are
˚
between 2.03 and 2.04 A, with Ru–P and Ru–C(cp) dis-
7
FcC„CC„CH with Na[BPh ] in the presence of
NEt was attempted. The product was an orange solid
characterised as [Ru{C„CC(NEt )‚CHFc}(dppe)-
4
tances ranging between 2.2445 and 2.3129(8), and 2.21 –
8
˚
2.24 A, respectively. Angles subtended at ruthenium by
6
3
3
Cp][BPh ] (8) by an X-ray structural study. Spectroscopic
4
the two P atoms and by the pair of P,C atoms are con-
sistent with the pseudo-octahedral arrangement of lig-
ands and depend on the bite angles of the ligands. For
dppe, P(1)–Ru–P(2) and P(1,2)–Ru–C(1) are between
81.32–83.87(3)ꢁ and 81.5–98.5(1)ꢁ, respectively, while
for dppm, P(1)–Ru–P(2) is 71.93(4)ꢁ.
ꢀ
1
properties include m(CC) bands at 2039 and 1596 cm
,
and Cp resonances at d 4.06 (Fe) and 4.83 (Ru), dC
H
3
9.04 and 83.38; the P NMR spectrum contained the
1
6
dppe resonance at d 86.90. The parent cation was found
at m/z 900 in the ES-MS.

M.I. Bruce et al. / Journal of Organometallic Chemistry 689 (2004) 2860–2871
2863
Fig. 1. Projection of molecules down the Cp(centroid)-Ru line: (a) Ru(C„CC„CFc)(dppe)Cp (1); (b) Ru(C„CC„CFc)(dppm)Cp (2);
c) Ru{C„CC Fc[Co (l-dppm)(CO) ]}(dppe)Cp (4); (d) Ru{C„CC Fc[Co (CO) ]}(PPh Cp (5).
(
2
2
4
2
2
6
3 2
)
Of most interest in the present study is the diynyl lig-
and. The diynyl nature of the carbon chain is shown by
amples [14]. In the isomeric complexes 6 and 7, addition
of tcne to one of the C„C triple bonds has resulted in
formation of tetracyanobutadiene fragments, character-
ised by C–C bond lengths ranging between
1.358–1.378(5) (C‚C), 1.483 and 1.491(4) (C–C), and
the short–long–short CC bond sequences [1.225(2),
˚
1.375(3) and 1.213(3) A], which compare well with those
in similar complexes [2] and in buta-1,3-diyne itself
˚
1.2176(14), 1.384(2) A] [15]. Angles at individual car-
˚
[
1.414–1.451(5) A (C–CN). In 6, in which addition to
the C„C triple bond adjacent to the ruthenium has oc-
bons C(1–4) are close to linear [range 170.5–178.9(4)ꢁ],
with a cumulative bend of ca. 20 (dppe), 6.9ꢁ (dppm).
As can be seen from the plots of 1 and 2, the overall
bending results in a displacement of the terminal carbon
˚
curred, the Ru–C(1) distance is 2.046(3) A, which is
2
within the normal range for an Ru–C(sp ) bond. In con-
˚
trast, in complex 7, Ru–C(1) is short [at 1.915(4) A] and
˚
˚
C(1)–C(2) is long [at 1.230(5) A], suggesting a contribu-
such that the Mꢁ ꢁ ꢁC(4) distances [5.235(4) (1), 5.771(8) A
(
distances [5.765(4), 5.943(8) A, respectively].
2)] are significantly less than the sum of the interatomic
˚
tion from the allenylidene tautomer 7a, induced by the
presence of the strongly electron-withdrawing polycy-
ano-olefinic substituent on C(2) and resulting in a degree
of multiple-bond character in the Ru–C(1) bond. These
features have been discussed above in connection with
In 4 and 5, addition of the Co fragment to the outer
2
C„C triple bond has resulted in the usual C–C bond
˚
lengthening [to 1.34(1) A] and bending about C(3) and
3
1
C(4) [angles C(2)–C(3)–C(4) 148.7(13)ꢁ, 144.1(5); C(3)–
C(4)–C(401) 136.1(10)ꢁ, 139.3(6)ꢁ, for 4 and 5, respec-
tively]. Other bond parameters for the Ru(dppe)Cp, Fc
and Co (l-dppm)(CO) fragments are not significantly
the assignments of the P NMR spectra.
Addition of tcne to transition metal alkynyl and poly-
ynyl complexes is a well-known reaction which has been
reported for complexes containing W [16], Fe [17], Ru
[18], Ni [19] and Pt [20]. It is considered to proceed via a
2
4
different from those found in many other reported ex-

2864
M.I. Bruce et al. / Journal of Organometallic Chemistry 689 (2004) 2860–2871
CN(22)
1
22
112
122
1
12
1
21
402
02
CN(21)
Fe
403’
4
02’
1
11
403
4
02’
P(1)
121
02
403
2
4
01’
403’
05’
P(1)
402
Fe
1
02
111
401’
1
4
4
04
1
01
10
1
0
405
4
401
1
CN(32)
Ru
1
03
404’
103
3
4
405’
Ru
1
05
2
04
0
1
2
405
2
0
1
CN(12)
212
105
0
1
104
0
4
P(2)
222
P(2)
212
211
221
CN(11)
CN(41)
221
222
211
CN(42)
(
a)
(b)
403
4
02
404
403’
401
Fe
112
322
1
21
4
05’
4
311
1
22
4
02’
3
22
404’
111
N(3)
401’
321
312
P(1)
4
4
04’
05
401’
402’
1
22
3
102
10
101
112
2
331
332
1
21
2
Fe
3
403"
312
1
Ru
1
02
1
03
2
1
111 P(1)
0
404
N(3)
101
4
311
1
103
0
1
05
P(2)
11
104
I(1)
403
331
402
Ru
212
2
212
105
222
20
221
332
104
21
P(2)
211
2
222
(
c)
(d)
Fig. 2. Projection of molecules down the Cp(centroid)-Ru line: (a) Ru{C[‚C(CN)
2
]C[‚C(CN)
2
]C„CFc}(dppe)Cp (6); (b) Ru{C„CC[‚C(CN)
2
]
CFc‚C(CN) }(dppe)Cp (7); (c) [Ru{C„CC(NEt )‚CHFc}(dppe)Cp]BPh (8); (d) [RuI(dppe){g-C
2
3
4
5
H
4
C„CC(NEt )‚CHFc}]I (9) (cations only).
3
3
radical intermediate which evolves successively to a tetra-
cyanocyclobutenyl derivative and, via a conventional
ring-opening reaction, to the isomeric tetracyanobutadie-
nyl derivative. The radical has notbeenfullycharacterised
and in the present instance, evidence for its formation was
seen in the short-lived deep green colouration which de-
veloped upon addition of tcne to the solution of 1, and
which rapidly faded at r.t. However, the cyclobutenyls
were not observed during the present reaction (spot
t.l.c.), presumably because of their rapid transformation
to the butadienyls. Recently, similar reactions between
tcne and ethynylferrocene, diferrocenylethyne and 1,4-
diferrocenylbuta-1,3-diyne to give the corresponding sub-
stituted s-cis-butadienes have been described [21].
The formulations of the cations in 8 and 9 were re-
vealed by the structural determinations. While the C4
group (on Ru in 8, and on the C ring in 9) is the
5
same, differences in C(1)–C(2) bond lengths [1.230(5),
˚
1.198(5) A, respectively] suggest that there is a contri-
bution from the allenylidene tautomer in the former.
This is supported by the relatively short Ru–C(1) dis-
˚
tance of 1.973(3) A. Effects of this formulation can be
traced through to the C(3)–N(3) separation, which is
˚
1.526(4) A in 8, but only 1.510(5) A in 9.
˚
The transfer of the alkynyl group from ruthenium in 8
to the Cp ring in 9, which occurs during the reaction with
iodine, has several precedents with alkyl-transition metal
complexes. Thus, the base-induced migration of organic

Table 1
Selected bond distances (A) and angles (ꢁ)
˚
Compound
1
2
4
5
6
7
8
9
˚
Bond distances (A)
Ru–P(1)
Ru–P(2)
2.2477(9)
2.2551(9)
2.261(1)
2.265(1)
2.251(4)
2.248(4)
2.313(2)
2.305(2)
2.2899(8)
2.3129(8)
2.257(1)
2.2445(8)
2.2540(9)
2.2626(8)
2.2915(9)
2.2654(8)
Ru–C(cp)
Ææ
Fe–C(cp)
2.237–2.251(4)
2.246(6)
2.029–2.050(4),
2.232–2.259(5)
2.245(13)
2.025–2.051(6)
2.22–2.26(1)
2.24(2)
2.02–2.04(1)
2.213–2.254(7)
2.23(2)
2.230–2.243(4)
2.237(5)
2.219–2.244(4)
2.23(1)
2.224–2.249(3)
2.24(1)
2.021–2.059(3)
2.189–2.255(4)
2.22(2)
2.04, 2.03(1),
2.036(11)
2.04(1), 2.03(1);
2.036(11)
2.047(6)
2.007–2.063(4),
2.033–2.044(4)
2.04(2), 2.038(5);
2.039(15)
2.016–2.046(4),
2.028–2.048(4)
2.03(1), 2.038(8);
2.04(1)
2.028–2.054(4),
2.024–2.070(5)
2.04(1), 2.05(2);
2.04(2)
2
.041–2.060(6)
2.037(8), 2.047(8);
.042(9)
b
a
Ææ
2.042(8), 2.040(10);
2.041(9)
2.030(9), 2.019(5);
2.024(9)
2.03(2) [2.05(8)] ;
–
2
Fe–C(401)
Ru–C(1)
2.050(3)
1.979(4)
1.225(5)
1.373(5)
2.007(3)
2.046(3)
2.028(4)
1.915(4)
2.059(3)
1.973(3)
1.219(4)
1.413(4)
1.526(4)
1.346(4)
1.459(4)
1.988(3)
1.227(5)
1.360(5)
1.963(10)
1.24(1)
1.40(1)
1.987(6)
1.216(8)
1.391(8)
2.7324(4) [I]
1.198(5)
1.426(5)
1.510(5)
1.349(5)
1.456(5)
C(1)–C(2)
C(2)–C(3)
C(3)–N(3)
C(3)–C(4)
C(4)–C(401)
C–CN
1.483(4)
1.403(5)
1.230(5)
1.377(6)
1.378(5) [C(03)]
1.491(4)
1.439(5)
1.188(5)
1.426(5)
1.214(6)
1.430(6)
1.34(1)
1.48(2)
1.348(8)
1.202(5)
1.409(5)
1.430–1.451(4)
1.414–1.434(5)
Bond angles (ꢁ)
P(1)–Ru–P(2)
82.77(3)
88.6(1)
84.1(1)
71.93(4)
88.2(1)
81.5(1)
83.4(1)
81.9(4)
100.82(6)
91.1(2)
89.1(2)
83.22(3)
98.50(9)
93.56(8)
118.8(2)
117.0(3)
83.44(3)
88.4(1)
83.87(3)
91.86(9)
84.11(8)
174.7(3)
171.3(3)
112.0(2)
126.4(3)
121.6(2)
122.7(3)
81.32(3)
87.57(2) [I]
95.03(2) [I]
P(1)–Ru–C(1)
P(2)–Ru–C(1)
Ru–C(1)–C(2)
C(1)–C(2)–C(3)
C(2)–C(3)–N(3)
C(2)–C(3)–C(4)
C(4)–C(3)–N(3)
C(3)–C(4)–C(401)
91.7(4)
173.3(12)
177.0(15)
82.45(9)
178.6(2)
173.1(3)
170.5(4)
176.2(3)
178.9(4)
169.8(5)
178.5(6)
172.6(3)
122.6(3) [C(03)]
115.3(3)
175.9(4)
114.1(3)
124.9(3)
121.0(3)
128.1(3)
176.2(5)
179.0(5)
178.0(5)
174.6(5)
148.7(13)
136.1(10)
144.1(5)
139.3(6)
177.3(3)
179.1(3)
122.1(4) [C(03)]
115.4(3)
˚
For 4: Co(3)–Co(4) 2.483(3), Co(3)–P(3) 2.235(3), Co(4)–P(4) 2.178(3), Co(3)–C(3,4) 1.98, 1.96(1), Co(4)–C(3,4) 1.98, 1.92(1), P(3,4)–C(0) 1.85, 1.82(1) A, Co(3)–P(3)–C(0) 108.1, Co(4)–P(4)–C(0)
1
10.2(4), P(3)–C(0)–P(4) 105.0(5)ꢁ.
˚
For 5: Co(1)–Co(2) 2.467(1), Co(1)–C(3,4) 1.991, 1.988(6), Co(2)–C(3,4) 2.012, 1.953(6) A.
˚
For 6: C(1)–C(01) 1.361(4), C(2)–C(02) 1.367(4) A, Ru–C(1)–C(01) 126.7(2), C(1)–C(2)–C(02) 123.1(3), C(01)–C(1)–C(2) 114.3(3), C(3)–C(2)–C(02) 119.9(3)ꢁ.
˚
For 7: C(3)–C(03) 1.378(5), C(4)–C(04) 1.358(5) A, C(3)–C(4)–C(04) 117.9(3), C(04)–C(4)–C(401) 126.4(3)ꢁ.
˚
For 9: Ru–C(101) 2.255(3), C(1)–C(101) 1.416(5) A, C(101)–C(1)–C(2) 176.8(4)ꢁ.
Disordered ring.
a
b
Individual rings; global.

2866
M.I. Bruce et al. / Journal of Organometallic Chemistry 689 (2004) 2860–2871
Table 2
Electrochemical data
dend has a strong electron-releasing effect upon the sys-
tem. For the tcne adducts 6 and 7, two reduction waves
at ca. ꢀ0.9 and ꢀ1.1 V are consistent with delocalisation
of the added electrons onto the strongly electron-with-
drawing dicyanomethylene groups. Two oxidation proc-
esses at ca. +0.8 and +1.05 V are close in potentials to
those found for 1 and 2 and may relate to the conjugated
a
Complex
Potentials (V)
b
+0.32, +0.76, +0.94
b
+0.31, +0.73, +0.89
c
c
1
2
3
4
5
6
7
8
9
+0.45, +0.55, +0.76
+0.09, +0.36, +0.64
c
+0.43, +0.68, +1.11
Ru–C –Fc system present in all four complexes. In 8,
4
ꢀ1.08, ꢀ0.92, 0.87, 1.09
ꢀ1.16, ꢀ0.91, +0.79, +1.06
+0.44, +0.86
two waves are found at +0.44 and +0.86 V, whereas in
9
, which no longer contains the diynyl-derived ligand at-
+0.62
tached to the ruthenium centre, only one process occurs,
at +0.62 V. This can be compared with a value of +0.28
V for RuCl(dppe)Cp. It is not clear which centre is being
oxidised in 9.
a
2 2 4 4
1.0 mM solutions in CH Cl , 0.1M [NBu ]BF , r.t., Pt-dot
working, Pt counter and pseudo-reference electrodes (FcH/
[
+
FcH] =0.46 V).
b
Irreversible.
Quasi-reversible.
c
3
. Conclusions
fragments has been reported for systems such as Co(P-
Me ) Cp complexes bearing acyl groups [22] and transfer
of SiMe groups from iron [23] while similar reactions
This paper has described the syntheses of complexes
containing
bonded to Ru(L) Cp (L=PPh , L =dppm, dppe) frag-
a 4-ferrocenylbuta-1,3-diynyl ligand r-
3
2
3
2
3
2
leading to amination of the Cp ring are known [24]. Ex-
tensive studies of arene-molybdenum complexes [25] and
acyl-iron derivatives [26] have concluded that nucleophi-
lic attack at the metal centre results in migration of the
carbon ligand to the p-ring, followed by loss of H. A
closely related example is the reaction between Ru-
ments and their derivatisation by addition of
0
0
0
Co (CO) L (L =CO, L =dppm) or tcne to one of the
2
6
2
2
C„C triple bonds. In the case of tcne, evidence for stabi-
lisation of the carbenoid tautomer (7a) of one of the ad-
3
1
ducts was obtained from P NMR and X-ray structural
studies. The lack of addition of a second tcne molecule
to the diyne probably results from the cyano groups of ei-
ther first adduct removing electron density from the sec-
ond C„C triple bond so that the radical intermediate
cannot form.
(
C„CPh)(PPh ) Cp and C (CO Me) to give RuCl-
3
2
2
2
2
(
some process akin to alkyne metathesis has also occurred
PPh ) (g-C H C„CCO Me) during which, however,
3
2
5
4
2
[
27], while more recently, Lo Sterzo [28] has found either
palladium- or LiBu-induced migrations in several cyclo-
pentadienyl-metal carbonyl alkyls. In the present trans-
formation of 8 into 9, attack by iodide at the
ruthenium centre prompts the migration of the alkynyl
In related chemistry, the formation of a (vinylammo-
nio)alkynyl complex (8) suggests the intermediacy of
the cationic butatrienylidene [Ru(‚C‚C‚C‚CHFc)-
+
(dppe)Cp] ; further reaction of the cation with I resulted
2
substituent to the C ring.
5
in migration of the alkynyl group to the Ru–C ring to
5
give [RuI(dppe){g-C H C„CC (NEt )‚CHFc}]I (9).
5
4
3
3
2
.2. Electrochemistry
We have determined the cyclic voltammograms for
most of these complexes under standard conditions
CH Cl , 0.1 V/s, 25 ꢁC, 0.1M [NBu ]PF ) and the ob-
4. Experimental
4.1. General experimental conditions
(
2
2
4
6
served redox potentials are listed in Table 2. Several
one-electron processes are found, not all of which can
be associated with oxidation of the ferrocenyl nucleus.
As reported earlier [8], the oxidation potentials of a se-
ries of complexes Fc(C„C) W(CO) Cp (n=1–4), in-
All reactions were carried out under dry, high purity
argon using standard Schlenk techniques. Common sol-
vents were dried, distilled under argon and degassed be-
fore use.
n
3
crease by ca. 60 mV per C2 unit added. In these
complexes, the W(CO) Cp group does not exhibit any
4.2. Instrumentation
3
redox properties. For complexes 1 and 2, an irreversible
oxidation at ca. +0.3 V occurs, followed by two quasi-
reversible processes at ca. +0.75 and +0.9 V.
Infrared spectra were obtained on a Bruker IFS28
FT-IR spectrometer. Spectra in CH Cl were obtained
2
2
The Co (CO) (dppm) (n=0,1) adducts 3–5 show
2
using a 0.5 mm path-length solution cell with NaCl
windows. Nujol mull spectra were obtained from sam-
ples mounted between NaCl discs. NMR spectra were
6-2n
n
three processes, that for 4 (which contains the dppm lig-
and) occurring at significantly lower potentials than
those found for 3 and 5, suggesting that the dicobalt ad-
1
recorded on Bruker AM300WB or ACP300 ( H at

M.I. Bruce et al. / Journal of Organometallic Chemistry 689 (2004) 2860–2871
2867
1
00.13 MHz, C at 75.47 MHz, P at 121.50 MHz) in-
3
31
ꢀ1
1
3
struments. Samples were dissolved in CDCl , unless
2024m; other band at 1653w (br) cm
.
H NMR
(C D ): d 1.93–2.00, 2.40–2.50 (2· m, 2· 2H, CH ),
3.80 [t (J 1.8 Hz), 2H, Fe(C H )], 4.03 (s, 5H, FeCp),
5 4
3
6
6
2
otherwise stated, contained in 5 mm sample tubes.
Chemical shifts are given in ppm relative to internal
4.28 [t (J 1.8 Hz), 2H, Fe(C H )], 4.65 (s, 5H, RuCp);
4
5
1
tetramethysilane for H and C NMR spectra and ex-
13
6.95–7.00 (m, 6H, Ph), 7.07–7.14 (m, 4H, Ph), 7.23–
13
7.35 (m, 5H, Ph), 7.91–8.00 (m, 5H, Ph). C NMR
3
ternal H PO for P NMR spectra. ES-MS: VG Plat-
1
3
4
form 2 or Finnigan LCQ. Solutions were directly
infused into the instrument. Chemical aids to ionisation
were used as required [29]. Cyclic voltammograms were
recorded at 298 K as described in Table 2 using a PAR
model 263 apparatus, a saturated calomel electrode,
(C D ):
d
[Fe(C H )], 69.81, 70.13 (FeCp), 71.78 [Fe(C H )],
28.13–28.74 (m, CH2), 60.86, 67.93
6
6
5
4
5
4
77.77, 83.33 (RuCp), 95.19, 115.75 [t, J 25.2 Hz, C(1)],
128.89 (Ph), 129.81 (Ph), 131.80–131.94 (m, Ph),
134.14–134.28 (m, Ph), 136.96–137.63 (m, Ph), 142.29–
3
1
and ferrocene as internal calibrant (FeCp2/
[
142.91 (m, Ph). P NMR (C D ): d 85.97. ES-MS
6 6
+
(m/z): 798, M , 100. Anal. Calc. for C H FeP Ru: C,
45 38 2
+
FeCp ] =+0.46 V). Elemental analyses were per-
2
formed at the Centre for Micro-Analytical Services
CMAS), Belmont, Vic.
67.76; H, 4.80. Found: C, 67.02; H, 4.55%. M, 798.
(
4.6. Synthesis of Ru(C„CC„CFc)(dppm)Cp (2)
4
.3. Reagents
RuCl(dppm)Cp (98 mg, 0.162 mmol),
FcC„CC„CH (80 mg, 0.342 mmol) and K[PF ] (66
mg, 0.359 mmol) were heated overnight in refluxing
thf (20 ml) containing dbn (0.25 ml). After removal of
solvent, chromatography of the residue (basic alumina,
Tetracyanoethene, Na[BPh ] and KF (Aldrich) were
4
6
used as received. The compounds RuCl(PPh ) Cp [30],
2
3
RuCl(dppe)Cp [31], FcC„CC„CH [32] and
Co (l-dppm)(CO) [33] were prepared using the cited
methods.
2
6
Et O/hexane 3/7) afforded Ru(C„CC„CFc)(dppm)Cp
2
dppm)Cp (2) as an orange crystalline solid (35 mg, 28%).
IR (nujol): m(C„C) 2174m, 2030m; other band at
4
.4. Synthesis of FcC„CC„CSiMe3
A solution of LiNPri [from NHPri (2.5 mL, 10
mmol) and LiBu (4.0 mL of 2.5 M) solution in light pe-
ꢀ1
1
1
2
652m (br) cm . H NMR (d -toluene): d 3.80 [m,
8
2
2
H, Fe(C H )], 4.02 (s, 5H, FeCp), 4.18 [m, 2H,
5
4
Fe(C H )], 4.20–4.42 (m, 2H, CH ), 4.81 (s, 5H, RuCp),
5
4
2
troleum] in Et O (30 mL) was added to cis-
2
7
8
.12–7.20 (m, 2H, Ph), 7.28–7.46 (m, 13H, Ph), 7.95–
13
FcC„CCH‚CHCl (1.02 g, 3.77 mmol) in Et O (20
2
.01 (m, 5H, Ph). C NMR (d -toluene): d 49.96 [t,
8
mL) at ꢀ78 ꢁC. The mixture was stirred for 4 h at
J(CP) 22.6 Hz, CH ], 60.89, 67.79 [Fe(C H )], 69.96,
2
5
4
ꢀ
78 ꢁC and then allowed to reach r.t. After cooling
7
9
0.09 (FeCp), 71.69 [Fe(C H )], 77.86, 81.05 (RuCp),
5 4
again to ꢀ78 ꢁC, the solution was quenched with SiCl-
6.31, 114.95 [t, J(CP) 24.1 Hz, C(1)], 128.01–128.18
Me (2 mL, excess) and warmed to r.t. overnight.
3
(m, Ph), 129.26, 129.92, 132.17 [t, J(CP) 5.7 Hz, Ph],
Solvent was removed in vacuo and the residue taken
up in hexane and filtered. Chromatography of the
reduced residue (basic alumina, hexane eluant) afforded
FcC„CC„CSiMe3 (1.05 g, 90%) as an orange
solid, identified by comparison with the literature
133.26 [t, J(CP) 5.7 Hz, Ph], 135.94 [t, J(CP) 25.8 Hz,
Ph], 137.10–137.85 (m, Ph), 139.29 [t, J(CP) 19.2 Hz,
31
Ph]. P NMR (d -toluene): d 18.64. ES-MS (MeOH,
8
+
m/z): 807, [M+Na] , 100; 784, M , 36. Anal. Found:
+
C, 67.37; H, 4.68. Calc. (C H FeP Ru): C, 67.44; H,
36
4
4
2
[
34].
4.63%; M, 784.
4
.5. Synthesis of Ru(C„CC„CFc)(dppe)Cp (1)
4.7. Reaction of Ru(C„CC„CFc)(dppe)Cp with
A mixture of RuCl(dppe)Cp (1000 mg, 1.67 mmol),
KF (127 mg, 2.19 mmol), and FcC„CC„CSiMe3
Co
2
(CO)
8
(
(
550 mg, 1.80 mmol) was heated in refluxing MeOH
50 mL, also containing 1 drop of dbu, 0.1 mL water)
To a solution of Ru(C„CC„CFc)(dppe)Cp (80 mg,
0.100 mmol) in Et O (20 mL) was added Co (CO) (71
2
2
8
for 1 h. After cooling, the precipitate was filtered off,
washed with cold methanol and dried under vacuum.
The solid was taken up in a small amount of benzene
and purified by chromatography (50% ether/hexane, ba-
sic alumina) to afford Ru(C„CC„CFc)(dppe)Cp (1)
mg, 0.208 mmol) and the mixture was stirred at r.t. for
1 h. Solvent was removed in vacuo and the crude residue
purified by chromatography (10% acetone/hexane, basic
alumina) to afford Ru{C„CC Fc[Co (CO) ]}(dppe)Cp
2 2 6
(3) (92 mg, 81%) as a dark green solid. IR (nujol):
m(CO) 2077m, 2032s, 2018s, 2000s, 1976m; other band
(
430 mg, 57% based on recovered FcC„CC„CH) as
ꢀ1
1
a yellow-orange solid. Crystals were obtained from ben-
zene/hexane. FcC„CC„H (170 mg, 31%) was recov-
ered from the filtrate. IR (nujol) m(C„C) 2174m,
at 1599w (br) cm
2.65–2.90 (2· m, 2· 2H, CH
4.30 (s, 5H, FeCp), 4.38 [s, 2H, Fe(C
.
H NMR (C
), 4.10 [s, 2H, Fe(C
)], 4.77 (s, 5H,
6
D
6
): d 2.20–2.40,
H
5 4
)],
2
H
4
5

2868
M.I. Bruce et al. / Journal of Organometallic Chemistry 689 (2004) 2860–2871
RuCp), 6.91–7.38 (m, 14H, Ph), 7.93 (broad s, 6H, Ph).
3
(C H Co FeO P Ru): C, 60.50; H, 3.66%; M, 1210.
61 44 2 6 2
1
P NMR (d -toluene): d 87.22. ES-MS (MeOH, m/z):
IR (CH Cl ): m(C„C) 2077m, 2037s, 2012s; also
8
2
2
+
+
ꢀ1
1
1
084, M , 5; 801, [MꢀCo (CO) ] , 12; 593,
1606w cm
.
H NMR (C D ): d 4.26 (br s, 10H,
2
6
6
6
+
[
ses could not be obtained.
MꢀFcC Co (CO) ] , 100. Consistent elemental analy-
FeCp+RuCp), 4.41, 4.47 (2· s, C H ), 6.95–7.05 (m,
2
2
6
5
4
6H, Ph), 7.10–7.35 (br s, 21H, Ph), 7.53–7.65 (br s,
3
+
H, Ph). ES-MS (positive ion, m/z): 1210, M ; 883,
+
[
MꢀPPh –Cp] .
3
4
.8. Reaction of Ru(C„CC„CFc)(dppe)Cp with
Co (l-dppm)(CO)
2
6
4
C (CN)
.10. Reaction of Ru(C„CC„CFc)(dppe)Cp with
Ru(C„CC„CFc)(dppe)Cp (100 mg, 0.125 mmol)
and Co (l-dppm)(CO) (101 mg, 0.150 mmol) were
2
4
2
6
heated overnight in refluxing thf (25 ml). Solvent was
removed in vacuo and the crude residue was purified
by chromatography (basic alumina, 25% ether/hexane)
to afford Ru{C„CC Fc[Co (l-dppm)(CO) ]}(dppe)Cp
A mixture of Ru(C„CC„CFc)(dppe)Cp (100 mg,
0
.125 mmol) and C (CN) (16.1 mg, 0.125 mmol) was
2
4
initially dark green, but changed rapidly to red, after
which it was heated in refluxing thf (25 mL) for 1 h. Sol-
vent was removed in vacuo and the residue was purified
by chromatography (silica, dichloromethane) to afford a
2
2
4
(
4) (135 mg, 76%) as a black solid. Crystals from
Et O/hexane. IR (nujol): m(CO) 2032m, 2000m, 1979s,
2
ꢀ
1
952s, 1935m; other bands at 1585w, 1572w cm .
1
1
/1 mixture of isomers 6 and 7 (77 mg, 67%) which was
1
H NMR (C D ): d 2.37–2.57, 2.39–3.05 (2· m, 2·
6
6
further purified by fractional crystallisation (dichloro-
methane/cyclohexane) to give 6 and 7 as dark red (from
dichloromethane/hexane) and red solids (from acetone/
hexane) respectively.
2
Fe(C H )], 4.51 [t (J 1.8 Hz), 2H, Fe(C H )], 4.53 (s,
H, CH ), 3.15–3.36 (m, 3H), 4.29 [t (J 1.8 Hz), 2H,
2
5
4
5
4
5
Ph), 6.84–7.06 (m, 21H, Ph), 7.15–7.22 (m, 13H, Ph),
H, FeCp), 4.93 (s, 5H, RuCp), 6.65–6.77 (m, 7H,
6
(low R ): IR (CH Cl ): m(CN) 2223w, 2214w, 1995s;
f 2 2
1
1
3
7
.39–7.44 (m, 5H, Ph), 8.07–8.13 (m, 4H, Ph).
C
ꢀ1
other bands at 1531w, 1480m cm . H NMR (CDCl ):
3
NMR (C D ): d 27.33–27.93 (m, CH ), 34.71–35.23
6
6
2
d 2.00–2.50 (m, 4H, CH ), 3.55–3.58 [m, 1H, Fe(C H )],
2
5
4
[
t, J(CP) 19.8 Hz, CH ], 67.41 [Fe(C H )], 69.44
2 5 4
4
4
[
(
.17 (s, 5H, FeCp), 4.25–4.28 [m, 1H, Fe(C H )], 4.62–
5 4
(
FeCp), 69.76 [Fe(C H )], 82.92 (RuCp), 87.33, 88.22
5 4
.66 [m, 1H, Fe(C H ), 4.81 (s, 5H, RuCp), 4.98–5.01
5
4
[
(
t, J(CP) 12.8 Hz, C(1)], 91.65, 111.40, 127.15–127.29
m, Ph), 128.67 (Ph), 129.16 (Ph), 130.73–130.89 (m,
Ph), 131.30–131.44 (m, Ph), 132.56–132.73 (m, Ph),
m, 1H, Fe(C H )], 7.02–7.16 (m, 2H, Ph), 7.19–7.40
5 4
m, 8H, Ph), 7.45–7.62 (m, 8H, Ph), 7.78–7.88 (m, 2H,
13
Ph). C NMR (CDCl ): d 27.27–29.66 (m, CH ),
3
2
1
1
1
2
33.50–133.64 (m, Ph), 135.55 [t, J(CP) 15.6 Hz, Ph],
36.83 [t, J(CP)25.2 Hz, Ph], 137.75–138.42 (m, Ph),
39.19 [t, J(CP) 22.1 Hz, Ph], 142.13–142.82 (m, Ph),
2
7
1
1
1
1
8.69–28.92 (m, CH ),70.99, 71.22, 71.26, 71.76 (FeCp),
2
1.80, 73.44, 74.00, 74.31, 75.25, 85.94 (RuCp), 113.23,
14.87, 115.42, 115.71 (4· CN), 128.32–128.51 (m, Ph),
29.45, 130.09, 130.23, 130.30, 130.83, 131.85, 131.93,
3
1
04.36, 207.95 (CO).
P NMR (C D ): d 36.30
6 6
(
dppm), 86.35 (dppe). ES-MS (MeOH, m/z): 1435,
32.19, 132.26, 133.83, 134.61, 134.68, 138.48, 138.74,
31
+
M+Na] , 48; 1412, M , 100. Anal. Found: C, 63.00;
+
[
H, 4.40. Calc. (C H Co FeO P Ru): C, 62.95; H,
41.43, 145.17, 171.99. P NMR (d -benzene): d 84.28
6
7
4
60
2
4 4
[d, J 16.8 Hz], 85.4 [d, J 16.8 Hz]. ES-MS (MeOH + Na-
+
OMe, m/z): 949, [M+Na] . Anal. Found: C, 43.60; H,
4
.28%; M, 1412.
3
4.14; N, 6.05; M, 926.
.72; N, 1.03. Calc. (C H FeN P Ru): C, 66.17; H,
51 38 4 2
4
Cp (5)
.9. Synthesis of Ru{C„CC Fc[Co (CO) ]}(PPh )
2
2
6
3 2-
7 (high R ): IR (CH Cl ): m(CN) 2225w, 2213w,
f 2 2
1
ꢀ
175m; m(C„C) 1994s; other band at 1606w (br) cm .
2
1
In a reaction similar to the synthesis of 1,
RuCl(PPh ) Cp (108 mg, 0.149 mmol) was treated
with FcC„CC„CSiMe (50 mg, 0.162 mmol) in the
presence of KF (12 mg, 0.207 mmol) in MeOH (15
ml) containing dbu (1 drop). An orange solid was ob-
tained, but could not be satisfactorily purified. Further
reaction with Co (CO) (48 mg, 0.14 mmol) in Et O
H NMR (CDCl ): d 1.90–2.20 (m, 1H, CH ), 2.30–
3
2
2.70 (m, 3H, CH ), 4.36 ( s, 5H, FeCp), 4.51, 4.54, 4.59,
4.72 [4· s, 4· 1H, Fe(C H )], 4.91 (s, 5H, RuCp), 6.63–
3
2
2
3
5
4
6.69 (m, 2H, Ph), 7.11–7.74 (m, 16H, Ph), 7.98–8.04 (m,
1
3
2H, Ph). C NMR (CDCl ): d 26.98–27.50 (m, CH ),
3
2
29.31–29.69 (m, CH ), 31.92, 60.12, 70.99, 71.27 (FeCp),
2
71.58, 71.80, 72.11, 73.92, 86.04 (RuCp), 112.16, 113.17,
113.56, 116.54, 117.92 (4· CN), 127.65–132.17 (m, Ph).
2
8
2
(
10 ml) overnight was followed by removal of solvent
3
1
and chromatography of the residue on basic alumina.
Elution with acetone/hexane (1/9) gave green crystal-
line Ru{C„CC Fc[Co (CO) ]}(PPh ) Cp (5) (52 mg,
P NMR (C D ): d 66.06 (d, J 21.4 Hz), 82.34 (d, J
6 6
21.4 Hz). ES-MS (MeOH+NaOMe, m/z): 949,
+
[M+Na] . Anal. Found: C, 65.63; H, 3.77; N, 5.95. Anal.
2
2
6
3 2
2
MeOH. Anal. Found: C, 60.58; H, 3.54. Calc.
9% overall). Crystals were obtained from CH Cl /
Calc. (C H FeN P Ru): C, 66.17; H, 4.14; N, 6.05%;
51 38
2
2
4 2
M, 926.

Table 3
Crystal data and refinement details
Compound
Formula
1
2
4
5
6
7
8
9
C
45
H
38FeP
2
RuÆ
C
44
H36FeP
2
Ru
C
74
H60Co
2
FeO
4
P
4
Ru
C
61
H44Co
2
FeO
6
P
2
Ru
C
51
H
38FeN
4
P
2
RuÆ
C
0.5CH
51
H
38FeN
4
P
2
RuÆ
C
75
H
74BFeNP
2
Ru
C
51 4 2
H53FeI NP Ru
C
6
H
6
C
3
H
6
O
2 2
Cl
MW
Crystal system
Space group
875.78
Monoclinic
C2/c
783.64
Orthorhombic
P2
1411.97
Triclinic
1209.75
Monoclinic
P2 /c
983.84
Monoclinic
968.23
Monoclinic
P2 /n
1219.10
Monoclinic
1406.48
Monoclinic
P2 /c
ꢀ
2
1 1
2
1
P1
1
P2
1
/c
1
1
P2 /c
1
˚
a (A)
29.970(4)
9.240(1)
33.582(4)
9.1748(7)
18.739(1)
21.420(2)
11.365(3)
15.075(5)
19.756(6)
22.804(5)
13.240(3)
17.428(4)
9.6645(8)
25.760(2)
18.714(2)
14.548(3)
18.752(3)
16.520(3)
10.977(2)
16.463(2)
34.032(5)
11.800(1)
25.876(3)
16.559(2)
˚
b (A)
˚
c (A)
a (ꢁ)
b (ꢁ)
c (ꢁ)
102.747(5)
96.467(5)
108.560(5)
3068
114.392(3)
96.629(3)
101.012(2)
108.698(5)
92.212(4)
92.694(3)
˚
3
V (A )
8470
8
3683
4
5227
4
4573
4
4269
4
6146
4
5051
4
Z
2
ꢀ
3
D
c
(gcm
)
1.37
0.81
3
1.41
0.92
3
1.52
1.16
8
1.53
1.29
7
1.42
0.76
9
1.50
0.87
6
1.31
0.58
7
1.84
3.1
9
ꢀ
1
l (cm
)
Crystal size (mm) 0.13·0.09·0.08 0.38·0.26·0.18 0.19·0.18·0.16
min/max
0.37·0.32·0.05
0.87
50
0.38·0.18·0.10
0.89
60
0.24·0.16·0.11
0.84
60
0.38·0.24·0.12
0.81
62.5
0.18·0.14·0.08
0.79
70
T
0.74
0.86
0.74
2
h
max (ꢁ)
60
8119
75
50
N
tot
76200
8649 (0.039)
7878
29115
10739 (0.095)
6147
39836
60715
48117
46322
89059
N (Rint
)
12142 (0.056)
10011
0.054
9206 (0.048)
6066
0.050
13422 (0.065)
9845
0.049
12102 (0.067)
8445
0.046
18089 (0.051)
12131
0.047
22278 (0.053)
14516
0.042
N
R
o
0.041
0.059
0.087
0.106
R
w
0.093
0.061
0.064
0.057
0.050
0.046

2870
M.I. Bruce et al. / Journal of Organometallic Chemistry 689 (2004) 2860–2871
3
1
4
.11. [Ru{C„CC(NEt )‚CHFc}(dppe)Cp]BPh (8)
131.60–132.48 (m, Ph), 134.57–134.82 (m, Ph).
P
3
4
NMR (CDCl ): d 79.15. ES-MS (MeOH, m/z): 1026,
3
+
+
RuCl(dppe)Cp
FcC„CC„CH (79 mg, 0.338 mmol), and Na[BPh4]
(203
mg,
0.338
mmol),
M , 100; 900, [M+HꢀI] , 20. Anal. Found: C, 43.60;
H, 3.72; N, 1.03. Calc. (C H FeI NP Ru): C, 43.58;
2
51
53
4
(
in thf/NEt (10 ml, 1:1). Solvent was removed and the
163 mg, 0.463 mmol) were heated overnight at 45 ꢁC
H, 3.73; N, 1.00; M, 1026 (cation).
3
residue was taken up in the minimum amount of
CH Cl , and filtered into an excess of well-stirred
Et O. A yellow solid was filtered off, and washed with
4
.13. Structure determinations
2
2
2
Full spheres of diffraction data were measured at ca
53 K using a Bruker AXS CCD area-detector instru-
Et O and hexane to afford [Ru{C„CC(NEt3)
2
1
ment. Ntot reflections were merged to N unique (Rint
cited) after ‘‘empirical’’/multiscan absorption correction
‚
CHFc}(dppe)Cp]BPh4 (8) (314 mg, 75%). Crystals
were obtained from CH Cl /Et O. IR (nujol): m(C„C)
2
2
2
ꢀ1
1
. H
2
039s; other bands at 1596w (br), 1580w cm
(proprietary software), N with F > 4r(F) being used in
o
NMR (CDCl ): d 0.33 [t, J 6.6 Hz, 9H, Me], 2.24 [q, J
3
the full matrix least squares refinements. All data were
measured using monochromatic Mo Ka radiation,
k=0.71073 A. Anisotropic displacement parameter
forms were refined for the non-hydrogen atoms, (x, y,
6
5
5
.6 Hz, 6H, CH ], 2.30–2.60 (m, 4H, CH ), 4.06 (s,
H, FeCp), 4.27, 4.67 [2· s, 2· 2H, Fe(C H )], 4.83 (s,
2
2
5
4
˚
H, RuCp), 5.54 (s, 1H, ‚CH), 6.80–6.95 (m, 4H,
Ph), 7.00–7.17 (m, 12H, Ph), 7.20–7.50 (m, 20H, Ph),
1
z, U ) being constrained at estimated values. Conven-
iso H
3
7
.64–7.81 (m, 4H, Ph). C NMR (CDCl ): d 7.51
3
tional residuals R, R on jFj are quoted at convergence
w
(
NEt ), 28.06–28.67 (m, CH ), 51.52 (NEt ), 68.95
3
2
2 ꢀ1
2
3
[
weights: (r (F)+0.0004F ) ]. Neutral atom complex
[
Fe(C H )], 69.04 (FeCp), 69.31 [Fe(C H )], 79.20,
5 4 5 4
scattering factors were used; computation used the
XTAL 3.7 program system [35]. Pertinent results are
given in Figs. 1 and 2 (which show non-hydrogen atoms
with 50% probability amplitude displacement ellipsoids
and hydrogen atoms with arbitrary radii of 0.1 A) and
in Tables 1 and 3.
8
(
3.38 (RuCp), 101.61, 120.52, 121.65, 121.98, 125.52
br), 127.89, 128.28 (br), 128.83 (t, J 23.7 Hz), 129.41,
1
1
30.12, 130.64–130.78 (m, Ph), 132.69–133.83 (m, Ph),
3
1
40.93–141.47 (m, Ph), 163.18–165.15 (m, BPh4).
P
˚
NMR (CDCl ): d 86.90. ES-MS (MeOH, m/z): 900,
3
+
+
M , 28; 799, [MꢀNEt ] , 100. Anal. Found: C, 73.72;
3
Individual diversities in procedure are noted as fol-
lows:
H, 6. 01; N, 0.98. Calc. (C H BFeNP Ru): C, 73.89;
7
5
74
2
H, 6.12; N, 1.15; M, 900 (cation).
1
4
. The benzene solvent molecule was refined as a rigid
body.
. Weak, poor quality data would support meaningful
anisotropic displacement parameters for Ru, Co,
Fe, P.
4
.12. Reaction of [Ru{C„CC(NEt )‚CHFc}-
3
(
dppe)Cp]BPh with iodine
4
To
dppe)Cp]BPh (65 mg, 0.0534 mmol) in thf (10 mL) was
a
solution of [Ru{C„CC(NEt )‚CHFc}-
3
(
added iodine (56 mg, 0.220 mmol), and the mixture
4
5
7
. Data collection at 298 K.
. The dichloromethane molecule of solvation was mod-
elled as disordered about an inversion centre, C half-
weighted.
. Cp ring 40n was modelled as disordered over two sets
of sites, occupancies set at 0.5 after trial refinement.
was stirred for 20 min at r.t. Solvent was removed in va-
cuo and the residue was taken up in the minimum
amount of CH Cl , and filtered into an excess of well-
2
2
8
stirred Et O. The precipitate was collected upon a sinter
2
and washed successively with ether, methanol, ether,
and hexane to give [RuI(dppe){g-C H C„CC(NEt )‚
5
4
3
CHFc}]I (9) (55 mg, 73%) as a brick-red solid. Crystals
3
i
were obtained from CH Cl /EtOH or CHCl /Pr OH. IR
2
2
3
(
1
6
nujol): m(C„C) 2197m, 1979w (br); other bands at
ꢀ
1 1
608w, 1585w cm . H NMR (CDCl ): d 1.27 [t, J
5. Supplementary material
3
.6Hz, 9H, Me], 2.42–2.52 (m, 2H, CH ), 2.83–3.02
2
(
m, 2H, CH ), 3.64 [q, J 6.6Hz, 6H, CH ], 4.31 [broad
2
Full details of the structure determination (except
structure factors) have been deposited with the Cam-
bridge Crystallographic Data Centre as CCDC
222413–222419 (for 9, 8, 1, 4, 6, 7 and 2, respectively)
and 225496 (5). Copies of this information may be
obtained free of charge from The Director, CCDC, 12
Union Road, Cambridge CB2 1EZ, UK (fax: +44-
1223-336-033; e-mail: deposit@ccdc.cam.ac.uk or
www: http://www.ccdc.cam.ac.uk).
2
s, 8H, FeCp + Fe(C H )+‚CH], 4.52 [s, 2H,
Fe(C H )], 5.09, 5.50 [2· s, 2· 2H, Ru(C H )], 7.03–
7
5
4
5
4
5
4
.10 (m, 5H, Ph), 7.28–7.42 (m, 14H, Ph), 7.70–7.80
1
3
(
m, 5H, Ph). C NMR (d -acetone): d 8.61 (NEt ),
6 3
2
7
8
7.89–28.99 (m, CH ), 54.52 (NEt ), 70.37 (FeCp), 71.,
2 3
2.02 [2· Fe(C H )], 77.23, 78.43 [Ru(C H )], 80.70,
5
4
5
4
4.13, 88.13 [Ru(C H )], 89.34, 119.84, 128.41–128.53
5
4
(
m, Ph), 128.88–129.00 (m, Ph), 130.05, 130.25,

M.I. Bruce et al. / Journal of Organometallic Chemistry 689 (2004) 2860–2871
2871
Acknowledgements
(c) M.I. Bruce, B.W. Skelton, A.H. White, N.N. Zaitseva, J.
Organomet. Chem. 650 (2002) 188.
11] (a) R.D. Adams, O.-S. Kwon, B. Qu, M.D. Smith, Organome-
[
We thank the Australian Research Council for sup-
port of this work and Johnson Matthey plc, Reading,
UK, for a generous loan of RuCl ÆnH O. Provision of
tallics 20 (2001) 5225;
(
b) R.D. Adams, B. Qu, M.D. Smith, Inorg. Chem. 40 (2001)
3
2
2932;
mass spectra by Professor B.K. Nicholson (University
of Waikato, Hamilton, New Zealand) is gratefully ac-
knowledged. These studies were facilitated by travel
grants (CNRS, France, and ARC IREX, Australia).
(c) R.D. Adams, B. Qu, Organometallics 19 (2000) 2411.
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