Oxidation chemistry of metal-bonded C4 chains: A combined chemical, spectroelectrochemical, and computational study

Article abstract of DOI:10.1021/ja992002t

The known complex {Cp(PPh₃)₂Ru}₂(μ-C≡CC≡C) (3-Ph) and its PMe₃- substitution product {Cp(PPh₃)(PMe₃)Ru}₂(μ-C≡CC≡C) (3-Me) have been shown by cyclic voltammetry to undergo a series of four stepwise one-electron oxidation processes. Successive oxidation potentials (V) for the first three reversible processes of 3-Ph (3-Me) are -0.23 (-0.26), +0.41 (+0.33), and +1.03 (+0.97); the fourth, irreversible oxidation at +1.68 (+1.46) V is accompanied by chemical transformation followed by further oxidation. Chemical oxidation of 3-Ph with 1 or 2.5 equiv of AgPF₆ in CH₂Cl₂/1,2- dimethoxyethane gave the one- and two-electron oxidized species [3-Ph][PF₆] and [3-Ph][PF₆]₂, respectively. The chemical and electrochemical studies have been complemented by a series of detailed spectroelectrochemical experiments to obtain spectral data associated with the 3(n+) (n = 0-4) species from 1500 to 40 000 cm^-1, without necessitating the isolation of each individual species. Theoretical techniques have been employed in order to probe the structure of the conjugated all-carbon ligand at each stage of oxidation. Both the metal centers and the carbon atoms of the C₄ bridge are affected, with removal of electrons housed in MOs delocalized over all atoms of the Ru-C₄-Ru chain. Comparison of models with different ligand surroundings suggests that molecules containing strong electron-donating ligands should be more easily oxidized.

Full text of DOI:10.1021/ja992002t

J. Am. Chem. Soc. 2000, 122, 1949-1962
1949
Oxidation Chemistry of Metal-Bonded C Chains: A Combined
4
Chemical, Spectroelectrochemical, and Computational Study
Michael I. Bruce,*, Paul J. Low,†,§ Karine Costuas, Jean-Fran c¸ ois Halet,*
†,‡
|
,|
⊥
#
Stephen P. Best, and Graham A. Heath
Contribution from the Department of Chemistry, UniVersity of Adelaide, Adelaide, South Australia 5005,
Australia, Laboratoire de Chimie du Solide et Inorganique Mol e´ culaire, UMR CNRS 6511, UniVersit e´ de
Rennes 1, 35042 Rennes Cedex, France, School of Chemistry, The UniVersity of Melbourne, ParkVille,
Victoria 3052, Australia, and Research School of Chemistry, Australian National UniVersity,
Canberra, ACT 0200, Australia
ReceiVed June 14, 1999
Abstract: The known complex {Cp(PPh3)2Ru}2(µ-CtCCtC) (3-Ph) and its PMe3-substitution product
{
Cp(PPh3)(PMe3)Ru}2(µ-CtCCtC) (3-Me) have been shown by cyclic voltammetry to undergo a series of
four stepwise one-electron oxidation processes. Successive oxidation potentials (V) for the first three reversible
processes of 3-Ph (3-Me) are -0.23 (-0.26), +0.41 (+0.33), and +1.03 (+0.97); the fourth, irreversible
oxidation at +1.68 (+1.46) V is accompanied by chemical transformation followed by further oxidation.
Chemical oxidation of 3-Ph with 1 or 2.5 equiv of AgPF6 in CH2Cl2/1,2-dimethoxyethane gave the one- and
two-electron oxidized species [3-Ph][PF6] and [3-Ph][PF6]2, respectively. The chemical and electrochemical
studies have been complemented by a series of detailed spectroelectrochemical experiments to obtain spectral
n+
-1
data associated with the 3 (n ) 0-4) species from 1500 to 40 000 cm , without necessitating the isolation
of each individual species. Theoretical techniques have been employed in order to probe the structure of the
conjugated all-carbon ligand at each stage of oxidation. Both the metal centers and the carbon atoms of the C4
bridge are affected, with removal of electrons housed in MOs delocalized over all atoms of the Ru-C4-Ru
chain. Comparison of models with different ligand surroundings suggests that molecules containing strong
electron-donating ligands should be more easily oxidized.
Introduction
tion as potential molecular wires which are required for use in
the assembly of nanoscale electronic devices. Ligands based
1
0
Complexes which display ligand-mediated electronic effects,
including electron-transfer phenomena, have attracted a great
on linear polycarbon chains, Cn, have emerged as some of the
1
1,12
most efficient “wires” examined to date.
1-3
deal of interest for many years. Many of the pioneering efforts
in this area played an important role in establishing various
aspects of mechanistic chemistry4 and in unraveling some of
the key steps in complicated biological reactions, including
respiration and photosynthesis. More recently, research in this
area has focused on the potential applications of these com-
pounds in the preparation of advanced materials which display
Polycarbon moieties based on yndiyl (-CtC-) and polyyndiyl
-{CtC}n-) motifs are remarkably versatile building blocks
(
,5
for use in the assembly of polymetallic structures due to their
unmatched ability to coordinate to metals in either σ- or
π-fashion or a combination of both. In light of the diverse
bonding modes available to polycarbon ligands it is hardly
surprising that an equally diverse range of metal-containing
groups has been attached to these ligands and there are many
examples of complexes in which carbon molecules of various
6
7-9
unusual magnetic or nonlinear optical properties.
capable of mediating electronic effects are also under investiga-
Ligands
†
13,14
University of Adelaide.
Tel: +61 8 8303 5939. Fax: +61 8 8303 4358. E-mail: michael.
lengths are coordinated to multinuclear cluster frameworks.
‡
However, most of the recent interest in the coordination
chemistry of Cn ligands has been focused on structurally simpler
complexes with greater potential for use in the realm of material
bruce@adelaide.edu.au.
§
Present address: Department of Chemistry, University of Durham,
South Road, Durham DH1 3LE, England.
|
Universit e´ de Rennes 1.
University of Melbourne.
Australian National University.
⊥
(9) Whittall, I. R.; McDonagh, A. M.; Humphrey, M. G.; Samoc, M.
AdV. Organomet. Chem. 1998, 42, 291; 1999, 43, 349.
#
(
1) Allen, G. C.; Hush, N. S. Prog. Inorg. Chem. 1967, 8, 357.
(10) (a) Atomic and Molecular Wires; Joachim, C., Roth, S., Eds.;
Kluwer: Dordrecht, The Netherlands, 1997. (b) Molecular Electronics:
Science and Technology; Aviram, A., Ratner, M. A., Eds.; Annals of the
New York Academy of Sciences, Vol. 852; New York Academy of
Sciences: New York, 1998. (c) Diedrich, F.; Rubin, Y. Angew. Chem. 1992,
104, 1123; Angew. Chem., Int. Ed. Engl. 1992, 31, 1101. (d) Lang, H.
Angew. Chem. 1994, 106, 569; Angew. Chem., Int. Ed. Engl. 1994, 33,
547. (e) Arnold, D. P.; Heath, G. A.; James, D. A. New J. Chem. 1998, 22,
1377. (f) Arnold, D. P.; Heath, G. A.; James, D. A. J. Porphyrins
Phthalocyanines 1999, 3, 5.
(2) Brown, D. M., Ed. Mixed-Valence Compounds; D. Reidel: Dordrecht,
The Netherlands, 1980.
(
(
(
(
3) Robin, M. B.; Day, P. AdV. Inorg. Chem. Radiochem. 1967, 10, 247.
4) Taube, H. Chem. ReV. 1952, 50, 69.
5) Haim, A. Prog. Inorg. Chem. 1983, 30, 273.
6) For examples and lead references see: (a) Ung, V. A.; Cargill
Thompson, A. M. W.; Bardwell, D. A.; Gatteschi, D.; Jeffery, J. C.;
McCleverty, J. A.; Tolti, F.; Ward, M. D. Inorg. Chem. 1997, 36, 3447. (b)
Cargill-Thompson, A. M. W.; Gatteschi, D.; McCleverty, J. A.; Navas, J.
A.; Rentschler, E.; Ward, M. D. Inorg. Chem. 1996, 35, 2701.
(11) Paul, F.; Lapinte, C. Coord. Chem. ReV. 1998, 178-180, 431.
(12) (a) Frapper, G.; Kertesz, M. Inorg. Chem. 1993, 32, 732. (b) Osella,
D.; Milone, L.; Nervi, C.; Ravera, M. Eur. J. Inorg. Chem. 1998, 1473.
(
7) Ward, M. D. Chem. Soc. ReV. 1995, 121.
(8) Long, N. J. Angew. Chem., Int. Ed. Engl. 1995, 34, 21.
1
0.1021/ja992002t CCC: $19.00 © 2000 American Chemical Society
Published on Web 02/17/2000

1950 J. Am. Chem. Soc., Vol. 122, No. 9, 2000
Bruce et al.
may be generated by oxidation of a single polyyndiyl complex
(structure A) must therefore be considered.
While our initial studies in this area were concerned with
the synthesis and reactivity of cluster-bound carbon molecules,14
some of our more recent efforts have been directed toward a
study of the synthesis and reactivity of complexes containing
mononuclear metal fragments. We have described the prepara-
tion of the parent diynyl complexes {MLn}(CtCCtCH) and
have demonstrated various methods by which the diynyl ligand
may be elaborated to give both substituted diynyl complexes
Figure 1. Valence-bond structures of all-carbon ligands bridging two
metal centers.
{
MLn}(CtCCtCR) and diyndiyl complexes {LnM}(µ-
2
2
CtCCtC){M′L′m}.
science. The compounds {MLx}-Cn-{M′L′y}, in which the
polycarbon chain is stabilized by interactions with just two metal
centers form one such class. For even-numbered carbon chains,
three configurations (excluding radical formulations) may be
written (Figure 1, structures A-C). For compounds which
feature an odd number of carbon atoms in the chain, at least
one of the metal centers must be involved in an M-C multiple
bond (Figure 1, structures D and E).
The diyndiyl complexes {Cp*(PPh3)(NO)Re}2(µ-CtCCtC)
1) and {Cp*(dppe)Fe}2(µ-CtCCtC) (2) have recently been
(
Experimentally, even-numbered carbon chains with predomi-
nantly polyyndiyl character (A) have been most commonly
observed. However, it should be noted that through judicious
choice of both metal-ligand combination and metal formal
oxidation state, it has been possible to isolate examples of
complexes with structures A, B, or C, e.g. for n ) 1, (Et3P)2-
1
5
prepared and their oxidation chemistry explored by Gladysz
2
0
and Lapinte and their respective co-workers. Both 1 and 2
undergo two reversible one-electron oxidation processes, evi-
denced by cyclic voltammetry. The large differences in the first
two redox potentials for these complexes [∆E° ) 0.53 (1), 0.72
V (2)] indicate that there are strong interactions between the
metal centers. The metal centers in 1 are chiral, and both
diastereomers of 1 have been oxidized by treatment with AgPF6
in the appropriate stoichiometry to give the PF6 salts of [(SS/
16
t
t
ClPt-CtC-Pt(PEt3)2 (A), (Bu SiO)3TadCdCdTa(OSiBu 3)3
1
7
t
t
18
(
B), and (Bu O)3W-CtC-W(OBu )3 (C). Several interme-
diate structures associated with the presence of metal end-
capping groups in dissimilar oxidation states
transfer processes have also been reported. Recently, several
subsets of these compounds have been subjected to high-level
theoretical treatments in order to arrive at a more detailed
15,19,20
or electron-
2
1
+
+
2+
2+
RR)-1] and [(SR/RS)-1] and [(SS/RR)-1] and [(SR/RS)-1] ,
with the retention of chirality at the metal centers in each case.15
12,15,17,19
description of their various electronic structures
In
+
The oxidized species [2][PF6] and [2][PF6]2, containing the 2
principle, structures A-C are related by a series of two-electron
steps
2
+
and 2 cations, respectively, have been obtained through
chemical oxidation of 2 with 1 or 2 equiv of [FcH][PF6].20
While the carbon ligands in the neutral forms of both 1 and
2
have been shown to have 1,3-diacetylenic character (M-Ct
CCtC-M, A) through various combinations of crystallographic
15
[
Re-C 2.037(5), CtC 1.202(7), C-C 1.389(5) Å ] and
1
5
spectroscopic [ν(CtC) 1968 w (1, KBr), 1955 m and 1880
2
0
w (2, Nujol) ] methods, there appear to be significant differ-
ences in the nature of the carbon bridges in the oxidized forms
+
+
2+
2+
1
vs 2 and 1 vs 2 . It has been established that there is a
and the possibility that the complete range of structures A-C
significant reduction in the CtC bond order, with a corre-
sponding increase in the C-C bond order, along the carbon
(13) See, for example: (a) Akita, M.; Moro-oka, Y. Bull. Chem. Soc.
+
bridge of 1 (Figure 1, structure A) upon oxidation to 1 and
Jpn. 1995, 68, 420. (b) Koutsantonis, G. A.; Selegue, J. P.; Wang, J.-G.
Organometallics 1992, 11, 2704. (c) Jensen, M. P.; Phillips, D. A.; Sabat,
M.; Shriver, D. F. Organometallics 1992, 11, 1859. (d) Elder, S. M.;
Robinson, B. H.; Simpson, J. J. Organomet. Chem. 1990, 398, 165. (e)
Norton, D. M.; Stern, C. L.; Shriver, D. F. Inorg. Chem. 1994, 33, 2701.
2
+
1 . Crystallographic evidence indicates that the carbon ligand
in [1][PF6]2 is best described by a cumulenic structure (Figure
1
5
+
1
, structure B). In contrast, the spectral data from 2 (as well
2
+
(14) (a) Bruce, M. I. J. Cluster Sci. 1997, 8, 293. (b) Bruce, M. I. Coord.
as crystallographic methods in this case) and 2 are consistent
Chem. ReV. 1997, 166, 91. (c) Adams, C. J.; Bruce, M. I.; Horn, E.; Skelton,
B. W.; Tiekink, E. R. T.; White, A. H. J. Chem. Soc., Dalton Trans. 1993,
with the retention of diacetylenic nature in the bridging C4
20
ligand. The unpaired electron in the monooxidized radical
3
299.
15) Brady, M.; Weng, W.; Zhou, Y.; Seyler, J. W.; Amoroso, A. J.;
Arif, A. M.; Bohme, M.; Frenking, G.; Gladysz, J. A. J. Am. Chem. Soc.
997, 119, 775.
16) Ogawa, H.; Onitsuka, K.; Joh, T.; Takahashi, S.; Yamamoto, Y.;
Yamazaki, H. Organometallics 1988, 7, 2257.
17) Neithamer, D. R.; LaPointe, R. E.; Wheeler, R. A.; Richeson, D.
S.; Van Duyne, G. D.; Wolczanski, P. T. J. Am. Chem. Soc. 1989, 111,
056.
+
cation 1 is delocalized over both the metal centers and the C4
(
chain; participation of the C4 chain is not established in the
1
+
case of 2 .
(
More recently, Lapinte and his colleagues have reported a
(
related study on the electron-rich complex {Cp*(dippe)Fe}2(µ-
i
i
C4) (dippe ) PPr 2CH2CH2PPr 2) and the sequential chemical
oxidation of this species by 2 equiv of [FcH][PF6] and 1 equiv
of AgPF6 to give the 33-electron species [{Cp*(dippe)Fe}2(µ-
9
(
(
18) Listemann, M. L.; Schrock, R. R. Organometallics 1985, 4, 74.
19) Belanzoni, P.; Nazzareno, R.; Sgamellotti, A.; Floriani, C. J. Chem.
2
3
Soc., Dalton Trans. 1998, 1825.
20) Le Narvor, N.; Toupet, L.; Lapinte, C. J. Am. Chem. Soc. 1995,
17, 7129.
21) Bruce, M. I.; Denisovich, L. I.; Low, P. J.; Peregudova, S. M.;
Ustynyuk, N. A. MendeleeV Commun. 1996, 200.
C4)][PF6]3. On the basis of crystallographic data and ESR,
(
1
(22) (a) Bruce, M. I.; Ke, M.; Low, P. J. Chem. Commun. 1996, 2405.
(b) Bruce, M. I.; Ke, M.; Low, P. J.; Skelton, B. W.; White, A. H.
Organometallics 1998, 17, 3539.
(

Metal-Bonded C4 Chains
J. Am. Chem. Soc., Vol. 122, No. 9, 2000 1951
Scheme 1
M o¨ ssbauer, and NIR spectroscopic evidence, a triradical struc-
ture featuring two Fe(III) centers and a carbon-centered radical
has been proposed for the trication.
Figure 2. Cyclic voltammograms of 3-Ph and 3-Me (CH
NBu ][BF ], 298 K, Pt working, counter and pseudo-reference
electrodes). [3-Ph (3-Me): E° -0.23 (-0.26); E° +0.41 (+0.33); E°
2 2
Cl , 0.1 M
[
4
4
1
2
3
+
3/4
+
We now take the opportunity to describe the characterization
+1.03 ( 0.97); E pa ≈ E°
4
+1.68 ( 1.46) V].
n+
of the complexes [{Cp(PPh3)(PR3)Ru}2(µ-CtCCtC)] [R )
5
Cp ligands in both the H (δ 4.43) and 13C (δ 82.71) NMR
spectra, while broad resonances associated with methyl groups
of the PMe ligands were observed in each case (δ 1.17, δ
1
Ph (3-Ph), Me (3-Me); Cp ) η -C5H5; n ) 0-4] containing a
bridging C4 ligand which can be obtained in an unprecedented
series of fiVe oxidation states. A combination of chemical,
spectroelectrochemical, and theoretical techniques have been
employed to determine the nature of the C4 ligand in each of
these oxidation states. A preliminary account of some of this
work has been published.21
3
H
C
22.50). A satisfactory microanalysis was also obtained.
In contrast to 3-Ph, for which three rotamers have been
2
4,26
crystallized to date,
it has not been possible to observe
distinct rotamers of 3-Me in either the solid state or in solution.
Presumably the decreased steric bulk about each metal center
in 3-Me, compared with 3-Ph, results in a much smaller degree
of interaction between the ligand spheres and consequently less
restricted rotation about the Ru-C(diyndiyl) bond. Furthermore,
it should be borne in mind that both metal centers in 3-Me are
stereocenters and it is reasonable to suggest that 3-Me exists as
a mixture of diastereomers. The NMR spectra collected from
samples of 3-Me prepared as described above were free of any
obvious line-doubling which might be expected to arise from
the presence of both RR/SS and RS/SR enantiomeric pairs, as
were the ν(CC) bands in the solid-state IR spectrum. The PMe3
proton resonance was significantly broadened, although this may
be attributable to the rotation processes indicated above rather
than as an indication of the presence of diastereomers. Despite
the success enjoyed by the Gladysz group in resolving RR/SS
and RS/SR forms of 1, exhaustive efforts to resolve samples of
Results
The known diacetylide-bridged diruthenium species {Cp-
(PPh3)2Ru}2(µ-CtCCtC) (3-Ph) is more conveniently obtained
in high yield from the reaction of RuCl(PPh3)2Cp with 0.5 equiv
of 1,4-bis(trimethylsilyl)buta-1,3-diyne, Me3SiCtCCtCSiMe3,
in the presence of a source of fluoride ion.2
4,26
Treatment of
3
-Ph with an excess of PMe3 in refluxing toluene afforded the
mixed phosphine complex {Cp(PPh3)(PMe3)Ru}2(µ-CtC-
CtC) (3-Me) in moderate yield (43%) (Scheme 1). The
exchange of the PPh3 ligands in Ru(CtCR)(PPh3)2Cp com-
plexes for other ligands, particularly phosphines with smaller
cone angles, has been well-documented.25 The mixed phosphine
complex 3-Me was characterized by a single ν(CtC) band in
-
1
the IR spectrum at 1974 cm and a parent ion at m/z 1056 in
the electrospray (ES) mass spectrum. The fragment ions
observed at higher cone voltages were also consistent with the
3
-Me by fractional crystallization were unsuccessful. In the
+
absence of single-crystal X-ray diffraction studies it is not
possible to prove the absolute configuration at the metals in
proposed formulation and included [Ru(PMe3)(PPh3)Cp] at m/z
5
05. A well-resolved singlet resonance was observed for the
3
-Me.
The cyclic voltammograms of 3-Ph and 3-Me were recorded
at 298 K in CH2Cl2/0.1 M [NBu4][BF4] and have been reported
(
23) Guillemot, M.; Toupet, L.; Lapinte, C. Organometallics 1998, 17,
928.
24) Bruce, M. I.; Hall, B. C.; Kelly, B. D.; Low, P. J.; Skelton, B. K.;
White, A. H. J. Chem. Soc., Dalton Trans. 1999, 3719.
25) Bruce, M. I.; Wong, F. S.; Skelton, B. W.; White, A. H. J. Chem.
Soc., Dalton Trans. 1981, 1398.
26) Bruce, M. I.; Hinterding, P.; Tiekink, E. R. T.; Skelton, B. W.;
White, A. H. J. Organomet. Chem. 1993, 450, 209.
1
(
2
1
previously. For convenience, these data are reproduced in
Figure 2. In each case three quasi-reversible (∆Ep ) 100 mV)
and one irreversible oxidation processes were observed, which
are consistent with the oxidation of the neutral diyndiyl
(
(

1952 J. Am. Chem. Soc., Vol. 122, No. 9, 2000
Bruce et al.
Scheme 2
complexes in four steps. As would be expected for 3-Me which
contains the more electron-donating PMe3 ligands, the formal
potentials for this complex are significantly less positive than
the corresponding redox processes in 3-Ph (i.e. the oxidations
of 3-Me are thermodynamically more favorable than the
corresponding oxidations of 3-Ph). No reductions were observed
within the solvent-imposed limit. The odd-electron species are
thermodynamically stable with respect to disproportionation, as
evidenced by the electrochemical data. For both 3-Ph and 3-Me,
all the redox processes are well separated, with the differences
in formal potentials, ∆E°, lying in the range 0.49-0.65 V.
While the first three oxidation processes were confirmed as
one-electron steps by comparison of the peak currents with that
of an equimolar internal ferrocene standard, the irreversible
fourth wave in the voltammogram appears to be a multielectron
wave by comparison of the peak currents. This may be taken
as an indication of the existence of an ECE mechanism in which
4+
the species 3 , once generated at the electrode surface,
undergoes a rapid chemical transformation to a new species,
which is then subject to a further oxidative process at the applied
potential.
Chemical oxidation of 3-Ph in dichloromethane with 1 equiv
of AgPF6 gave a deep green solution from which analytically
pure [3-Ph][PF6] was isolated as a dark green powder by
precipitation into diethyl ether. The ES mass spectrum of [3-Ph]-
+
[
PF6] was characterized by an intense [3-Ph] ion at m/z 1430.
-
1
A strong ν(CC) band was observed at 1861 cm , while the
ν(PF) band from the counterion was observed at 840 cm . Only
broad featureless resonances were observed in the H NMR
spectrum of [3-Ph][PF6] which suggests that the cation [3-Ph]
Figure 3. IR spectroelectrochemical spectra obtained following
oxidation of 3-Ph. The spectra were collected with a resolution of 4
-1
-
1
1
cm with time intervals of 1.6 s for (a) and (b) and 2.4 s for (c). In
each case the reference spectrum was recorded immediately prior to
the application of an oxidizing potential.
+
is paramagnetic.
Oxidation of [3-Ph][PF6] with a further 1 equiv of AgPF6,
or direct treatment of 3-Ph with 2.5 equiv of the same oxidizing
agent, afforded [3-Ph][PF6]2 as a dark blue microcrystalline solid
following conventional workup and crystallization. In contrast
to the monooxidized species, [3-Ph][PF6]2 gave well-resolved
NMR spectra. The Cp ligands gave rise to single sharp
work are described in the Experimental Section. In essence, the
spectra of the various oxidized species were obtained from
samples obtained by electrolysis of a small amount of solutions
of 3 trapped in a thin film in the region about the working
electrode. The working electrode was initially held at a resting
potential at which the neutral complex was stable. Guided by
the CV data, the applied potential was then increased to
1
13
resonances in both the H (δ 5.03) and C (δ 90.82) NMR
spectra. Unfortunately the 13C resonances from the carbon ligand
could not be observed, even with long pulse delays. The ES
mass spectrum of [3-Ph][PF6]2 at low cone voltages contained
the intense doubly charged ion [3-Ph]2 at m/z 715, with isotope
peaks separated by 0.5 amu, consistent with the dicationic nature
+
electrogenerate the monooxidized species 3 . The reversiblity
of the system under the conditions of the spectroelectrochemical
experiment was confirmed by electrochemical reduction of the
sample to give spectra identical to that of the precursor. The
+
n+
spectra of the higher oxidized species 3 were obtained by
-
1
of this species. The ν(CC) band was observed at 1766 cm .
The monooxidized species [3-Ph][PF6] was also obtained
from the comproportionation reaction of 3-Ph with [3-Ph][PF6]2,
as indicated in Scheme 2. It should also be noted that the CV
of each of [3-Ph][PF6] and [3-Ph][PF6]2 were identical with
that of 3-Ph measured under the same conditions. Unfortunately,
all attempts to obtain [3-Ph][PF6]3 by further chemical oxidation
were unsuccessful.
similar processes of electrolysis, and reversibility was established
(n-1)+
by quantitative reduction to the precursor 3
states.
IR spectra recorded during the progressive oxidation of 3-Ph
and 3-Me to their tricationic states are marked by a reduction
in the wavenumber of ν(CC) (Figure 3 and Table 1). In keeping
with their voltammetric response (Figure 2), oxidation and
rereduction occur reversibly and on a similar time scale. Further
oxidation to the tetracation is, at best, quasi-reversible, and
oxidation of the trications was examined at temperatures of -40
To collect more detailed information about the species
detected by cyclic voltammetry, a series of spectroelectrochemi-
cal experiments was carried out, covering the IR, NIR, visible,
and UV regions of the spectrum. The mid-IR spectra were
collected in a modifed infrared reflection absorption spectros-
copy (IRRAS) cell, while the samples for NIR/vis/UV spec-
troscopy were generated by electrolysis and analyzed in an
optically transparent thin-layer electrode (OTTLE) cell in situ.
°
C or lower. Under these conditions we were unable to convert
between the tri- and tetracations in the absence of significant
concentrations of the dication. Indeed, the predominant trans-
formation was between the di- and tetracations (Figure 4). The
-1
oxidation products, marked by a strong band at 1936 cm , may
(27) (a) Best, S. P.; Clark, R. J. H.; McQueen, R. C. S.; Clooney, R. P.
ReV. Sci. Instrum. 1987, 58, 2071. (b) Best, S. P.; Ciniawskii, S. A.;
Humphrey, D. G. J. Chem. Soc., Dalton Trans. 1996, 2945.
(28) Duff, C. M.; Heath, G. A. Inorg. Chem. 1991, 30, 2528.
Details of these experimental techniques have been given
previously,2
7,28
and only the particular details relevant to this

Metal-Bonded C4 Chains
J. Am. Chem. Soc., Vol. 122, No. 9, 2000 1953
Table 1. Mid-IR ν(CC) Absorptions (cm-1)
n ) 0
n ) 1
n ) 2
1767
1767
n ) 3 n ) 4
[
[
1
2
3-Ph]n+ a 1971, 1956 1855
1627 1936
1628 1928
n+ a
3-Me]
1972, 1957 1856
1964 1872
1880, 1955 1880, 1973 1950, 2160
n+ b
not obsd
n+ c
a
solution, 0.1 M [NBun ], -50 °C. b From ref
IRRAS, CH
2
Cl ][PF
2
4
6
1
5. c From ref 20.
Figure 4. IR spectroelectrochemical spectra of 3-Ph (initial potential
0.72 V) obtained following the application of a potential of (a) 1.8,
Figure 5. UV/vis/NIR spectra of (a) [3-Ph]0/+, (b) [3-Ph]+/2+, and (c)
)
-
1
2+/3+
(b) 2.3, and (c) 0.72 V (spectral resolution ) 4 cm ; time between
[3-Ph]
obtained from spectroelectrochemical experiments in an
spectra ) 2.4 s).
OTTLE cell (at -30 °C).
be rereduced with ca. 85% regeneration of the starting materials,
although the rate of oxidation is markedly faster than that of
rereduction (Figure 4b,c). Relatively large fluctuations in the
baseline are evident in experiments leading to the generation
of the tri- and tetracations, and this is likely to be due to the
deposition of a solid film on the electrode.
+
be noted at this point that the odd-electron species 3 (35-e)
3+
and 3 (33-e) are both formally mixed-valence compounds and
that no species corresponding to the quadruply-oxidized species
4+
3
has yet been observed during the oxidation of either 1 or 2.
The ∆E° values found for the redox processes reflect a large
degree of electronic interaction between the metal centers
through the C4 bridge. Since the equilibrium constant, Kc, for
the comproportionation reaction
The UV/vis/NIR spectroelectrochemical results are marked
by similarly well-defined spectral changes, with clean isosbestic
+
+
2+
2+ 3+
points marking the interconversions 3/3 , 3 /3 , and 3 /3
Figure 5, Tables 2 and 3). Owing to the much longer time
needed to perform the OTTLE experiments (ca. 8 min/scan) it
(
Mn]+[Mn+2] H 2 [Mn+1
[
]
(1)
4+
is given by the expression29
was not possible to obtain spectra of 3 .
Discussion
(n+1) 2
n
(n+2)
K ) [M
] /[M ][M
] ) exp[∆E°(F/RT)] (2)
c
Several rotamers of 3-Ph have been structurally character-
ized,2 and these studies, in conjunction with the ν(CtC) data
4,26
the electrochemical data allow the thermodynamic stabilities
of the various oxidized species to be assessed.
reported both here and elsewhere2
4,26
provide conclusive
+
evidence that the structure of the carbon ligand in the neutral
complex 3-Ph is best described in terms of a 1,3-diacetylene
type structure (Figure 6, structure A), as was observed for both
the rhenium and iron complexes 1 and 2.1 Both metal centers
in 3 may be regarded as formally Ru(II). The band due to
ν(CtC) in 3-Me is similar to that of 3-Ph, and the 1,3-
diacetylenic structure may also be assigned to the C4 ligand in
The Kc values calculated for the odd-electron species 3 ([3-
+
11
+
10
3+
3+
Ph] , 1.5 × 10 ; [3-Me] , 2.1 × 10 ) and 3 ([3-Ph] , 1.5
1
1
3+
8
× 10 ; [3-Me] , 2.7 × 10 ) are larger than has been found
for the well-known Creutz-Taube ion {Ru(NH3)5}2(µ-pyrazine)
5,20
6
.6
30
7.3
31
[Kc ) 10 (aqueous solution), 10 (acetonitrile solution) ]
and are comparable with the values previously reported for the
+
+
related species [{Cp*(NO)(PPh3)Re}2(µ-C4)] (1 ) (Kc ) 3 ×
8
15
+
+
12 20
3
-Me.
Given the differences in the electronic structures of the C4
bridges observed in the various oxidized forms of 1 and 2, i.e.,
10 ) and [{Cp*(dppe)Fe}2(µ-C4)] (2 ) (Kc ) 1.6 × 10 ).
The Kc values are large enough to allow the electrogenerated
(
(
29) Richardson, D. E.; Taube, H. Inorg. Chem. 1981, 20, 1278.
30) Creutz, C. Prog. Inorg. Chem. 1983, 30, 1.
+
+
2+
2+
1
vs 2 and 1 vs 2 , the nature of the carbon ligands in the
species formed by oxidation of 1 is of some interest. It should
(31) Creutz, C.; Chou, M. H. Inorg. Chem. 1992, 31, 3170.

1954 J. Am. Chem. Soc., Vol. 122, No. 9, 2000
Bruce et al.
Table 2. NIR IVCT Absorptions (cm-1)
max (cm-1)
ꢀ (M-1 cm-1
)
∆ν1/2 (obsd, cm-1
)
∆ν1/2 (calcd from eq 3, cm-1
)
H
AB (eV)
a
ν
b
[
3-Ph]+
11 400
11 100
7 541
8 000
13 400
12 000
3 200
9 400
15 000
900
3600
3200
3250
1500
1200
1800
3400
3000
5131
5063
4220
4166
5000
5663
5308
5264
0.71
0.69
0.47
0.516
0.620
0.702
0.76
+
c
[3-Me]
2
3
+ d
+ e
2
1
8 333
0 000
1 325
1
1
[
[
3-Ph]3
3-Me]
+ b
+ c
12 200
12 000
3
1 700
0.74
a
b
solution, 0.5 M [NBun
], -30 °C, sample concentration ) 7.0 × 10 M. c OTTLE cell,
-4
Also denoted Vab in ref 17. OTTLE cell, CH
2
Cl
2
4
][BF
4
n
], -30 °C, sample concentration ) 2.3 × 10 M. d From ref 20. e From ref 15.
-3
2 2 4 4
CH Cl solution, 0.5 M [NBu ][BF
Table 3. UV-Vis Absorptions [λmax, cm- (ꢀ, M-1 cm-1)]
1
n
[3-Ph]n+ a
[3-Me]n+ b
1n+ c
2n+ d
0
32 200 (7140)
29 600 (5290)
28 902 (20 500)
3
4
7 037 (31 000)
3 104 (65 000)
1
2
37 800 (27 700)
16 300 (45 400)
37 500 (50 500)
22 026 (6 400)
8 735 (24 000)
17 421 (30 000)
25 510 (41 000)
37 037 (25 000)
17 825 (700)
22 883 (4100)
2
16 790 (47 700)
18 800 (15 900)
36 000 (49 300)
1
3
8 500 (11 700)
2 900 (38 600)
4
2 735 (57 000)
3
17 300 (21 700)
18 450 (17 700)
29 500 (28 300)
37 000 (25 000)
2
3
7 500 (42 900)
6 400 (34 600)
a
n
], -30 °C, sample concentration ) 7.0 × 10 M. b CH
-4
solution, 0.5 M [NBun
][BF ],
4 4
OTTLE cell, CH
2
Cl
2
solution, 0.5 M [NBu
4
][BF
4
2
Cl
2
-
3
c
d
-
30 °C, sample concentration ) 2.3 × 10 M. From ref 15. From ref 20.
similar progression of ν(CC) to lower wavenumbers was
+
2+ 15
observed for 1, 1 , and 1 . Indeed, the similarity of the IR
+
+
data for 1 and 3 suggests that the structure of the carbon
+
ligand is similar in both cases. Each of the monocations 1 ,
, and 3 give rise to an IVCT band in the NIR region of the
+
+
2
spectrum (Table 2) which is characteristic of the formally mixed-
32
valence nature [M(II)/M(III)] of these compounds. In the case
+
of 3 the position of νmax was found to be virtually independent
+
of solvent ([3-Ph] 11 400 ( 50 (CH2Cl2), 11 300 ( 50
+
-1
(
MeCN); [3-Me] 11 050 ( 50 cm (CH2Cl2), 10 900 ( 50
-
1
cm (MeCN)]. In addition, the widths of the IVCT bands at
half-height (∆ν1/2) are considerably narrower than predicted
3
0,32
from the relationship in eq 3 (Table 2),
which has been
derived for complexes of class II in the well-known Robin-
3
,33
Day classification of mixed-valence systems.
1
/2
∆ν1/2 ) [2310νmax
]
(3)
On the basis of all of the above data, it can be safely
+
+
concluded that [3-Ph] and [3-Me] are Robin-Day class III
mixed-valence” compounds and that the unpaired electron is
“
delocalized over the Ru-C4-Ru six-atom fragment. The
complexes are therefore best described as containing two Ru
centers of intermediate oxidation state, rather than one localized
Ru(II) center and one localized Ru(III) center. The energy of
the IVCT band for class III complexes is related to the resonance
energy between the ground and excited states, HAB, by the
3
0,34,35
Figure 6. Elementary valence structures of 3n+ (n ) 0-4).
expression
HAB ) νmax/2
(4)
species to be obtained as pure materials without any contamina-
tion from higher or lower oxidation states.
+
+
The calculated values of HAB are given in Table 2. These values
Both [3-Ph] and [3-Me] contain a single ν(CC) band
approximately midway between the related neutral and dicationic
species (Table 1). This observation provides strong evidence
that the unpaired electron is delocalized over the molecule on
(
32) Hush, N. S. Prog. Inorg. Chem. 1967, 8, 391.
(33) Astruc, D. Electron Transfer and Radical Processes in Transition
Metal Chemistry. Part 1; VCH: New York, 1995.
(
34) Woitelier, S.; Launay, J. P.; Spangler, C. W. Inorg. Chem. 1989,
-
12
the IR time scale (ca 10 s) and, consequently, that the metal
2
8, 758.
+
centers in these odd-electron monocations 3 are equivalent. A
(35) Dong, Y.; Hupp, J. T. Inorg. Chem. 1992, 31, 3170.

Metal-Bonded C4 Chains
J. Am. Chem. Soc., Vol. 122, No. 9, 2000 1955
are large and as such are also entirely consistent with the class
+
III description of these complexes. The complexes 3 may be
therefore be described in terms of the series of simple valence
bond forms represented by structure B, Figure 6. An alternative
MO description is presented below.
1
Sharp, well-defined resonances were found in the H NMR
spectra of the isolated [3-Ph][PF6]2 complex, suggesting that
the cation is diamagnetic. In terms of a model in which the
oxidation processes are metal-based, this observation requires
spin-spin coupling between two Ru(III) sites. An alternative
model, in which the HOMO is not metal-centered but has
appreciable carbon character as well, can also be invoked, and
the diamagnetism of 32 is then simply explained in terms of
the removal of both electrons from this Ru-C4-Ru derived
HOMO and the return of the system to an S ) 0 spin-paired
ground state. Again, a more detailed discussion on this point is
deferred to the Theoretical section below. However, it should
be noted at this stage that the ν(CC) band is found at rather
low frequency, suggesting a cumulenic structure (Figure 6,
structure C) which, curiously, is more keeping with the nature
of the rhenium complex 12+ than of the iron analogue 2 .
+
n+
Figure 7. Plot of observed ν(CC) for [3-Ph] vs reciprocal of
n+
calculated C(R)-C(â) separations for [3-H] (Table 4).
for the central carbons of the bridge will contribute to the
Raman-active modes and formally will be IR-inactive.
A simple analysis of the linear Ru-C -C -C -C -Ru
system shows that the stretching modes along the chain axis
will result in three Raman, two infrared, and one translational
mode. Provided that coupling between the Ru-C and C -C
R R â
stretches is small, then the higher wavenumber IR-active
stretching mode along the chain axis will be dominated by the
2+ 15,20
R
â
â
R
The UV/vis spectra of [3-Ph]2+ and [3-Me] are dominated
2+
-
1
by a new feature at 33 000 or 37 000 cm , respectively, and
-
1
-1
intense transitions at 16 300 or 16 790 cm (ꢀ ca. 45 000 M
-
1
-1
cm ), with smaller shoulders near 18 500 cm in each case.
There are no comparable bands found in the spectra of either 3
+
2+
R â
C -C force constant. This being so, the wavenumber of the
or 3 , and therefore these features in the spectra of 3 are most
likely Ru-C(ligand) MLCT transitions.
ν(CC) mode observed in the IR spectroelectrochemical experi-
ments ought to correlate with the CR-Câ force constant or,
alternatively, the reciprocal of the CR-Câ bond length. The DF
calculations provide an estimate of this bond length (model 3-H,
Table 4), and an excellent linear correlation is obtained for the
neutral through tricationic species (Figure 7). Thus both the
wavenumber and intensity of the band obtained following further
The electrogenerated tricationic species 33 are characterized
+
-
1
by single, strong ν(CC) bands near 1627 cm , the observation
of which suggests a further decrease in the CtC bond order in
the C4 bridge. In keeping with their formal mixed-valence
Ru(IV)/Ru(III) composition, these species also give rise to
-
1
characteristic NIR bands near 12 000 cm , although the
3
+
oxidation of 3 are inconsistent with expectations based on
structure E, Figure 6. Since the species responsible for the 1936
cm band may, on a relatively rapid time scale, be reduced to
generate 3, it is unlikely that there is dissociation of the metal
centers from the C4 bridge. On the basis of the spectroscopy,
either a highly asymmetric structure and/or diacetylenic char-
acter in the C4 bridge may account for the 1936 cm band. As
mentioned above, this feature possibly arises from a complex
formed by rapid oxidation of some species resulting from rapid
chemical transformation of 3 ; we defer speculating on the
nature of this species until completion of further experiments.
intensities of these bands are much less than those found for
+
3
. In addition, MLCT bands were also observed (Figure 5c,
-1
Table 3). While the electrogenerated trications are thermo-
1
1
3+
8
3+
dynamically (Kc ) 1.5 × 10 , [3-Ph] ; 2.7 × 10 , [3-Me] )
and kinetically stable in CH2Cl2 at -50 °C, attempts to generate
3
+
3+
[
3-Ph] or [3-Me] in MeCN at low temperatures were
-1
complicated by the kinetic instability of these species in the
more nucleophilic solvent. However, while the solvent depen-
dence of these NIR bands cannot be easily assessed, assignment
4+
3
+
of 3 as a class III Robin-Day system may still be made by
noting that in addition to the single ν(CC) band and unique
UV/vis spectra, the ∆ν1/2 value is significantly smaller than the
Theoretical Analysis
+
value calculated from eq 3 (Table 2). As was the case with 3
To gain further insight into the electronic structure of the
binuclear ruthenium diyndiyl species 3 and the structural and
physical properties of the complexes formed upon oxidation,
extended H u¨ ckel (EH) and density functional (DF) molecular-
orbital calculations were carried out on the model complexes
{Cp(PH3)2Ru}2(µ-C4)] , [3-H] (n ) 0-4). Computational
details are given in the Experimental Section.
Qualitative Analysis. We commence with an analysis of the
neutral complex 3-H. A simple EH molecular orbital diagram
(Figure 8) is a useful aid in arriving at a qualitative understand-
ing of the bonding between the C chain and metallic end-caps.
Using a fragment analysis, the formation of 3-H can be
envisioned as a result of the interaction of the frontier molecular
orbitals (FMO) associated with the (C4) unit with those of
the bimetallic fragment [{Ru(PH ) Cp} ] . The charges on the
fragments have been chosen in such a way that the number of
electrons associated with the carbon atoms of the C4 fragment
3+
the values of HAB calculated for 3 from the NIR data are large
[3-Ph] , 0.76 eV; [3-Me] , 0.74 eV). These species may be
3
+
3+
(
described by structure D in Figure 6.
The quadruply-oxidized complexes 34 are highly reactive
and were only observed as transient species. The spectral
changes associated with further oxidation of [3-Ph]2 are shown
+
n+
n+
[
+
3
+
in Figure 4. In addition to the band associated with [3-Ph]
-
1
an intense feature grows into the spectrum at 1936 cm .
Rereduction of this solution results in substantial regeneration
of the starting products, indicating that the species responsible
4
-
1
for the 1936 cm band is chemically related to the starting
material. The wavenumber of this feature is reminiscent of
ν(CC) of an electron-deficient alkyne, and it is tempting to
attribute to it the ν(CC) of the species indicated by structure E
of Figure 6. This interpretation is unlikely, however, since for
the approximately centrosymmetric complex the ν(CC) band
2
-
2+
3
2
2

1956 J. Am. Chem. Soc., Vol. 122, No. 9, 2000
Bruce et al.
a
b
c
Table 4. Selected Optimized Bond Lengths (Å) and Bond Angles (deg), Relative Energies (Erel, eV), and Adiabatic Ionization Potentials
n+
n+
n+
n+
n+
n
(
IP, eV) for the Model Complexes [{Cp(PH
3
)
2
Ru}
(µ-C
2
(µ-C
4
)] , [3-H] , [{Cp*(PH
3
)
2
Ru}
(µ-C
2
(µ-C
4
)] , 4 , [{Cp(dHpe)Ru}
2
(µ-C )] , 5 +,
4
n+
n+
)] , 7n+, and [{Cp*(CO)
n+
)] , 8n+, (n ) 0-4)
n+
[
{Cp*(dHpe)Ru}
2
(µ-C
4
)] , 6 , [{Cp(CO)
2
Ru}
2
4
2
Ru}
2
4
model
Ru-C(R)
C(R)-C(â)
C(â)-C(â′)
Ru-C(R)-C(â)
C(R)-C(â)-C(â′)
E
rel
IP
3
-H
2.022
1.968
1.923
1.915
1.880
1.853
2.030
1.974
1.932
1.929
1.898
1.884
2.028
1.973
1.926
1.918
1.886
1.850
2.039
1.986
1.934
1.931
1.900
1.873
2.037
1.992
1.949
1.948
1.910
1.879
2.050
2.004
1.960
1.960
1.932
1.8
1.241
1.259
1.276
1.279
1.298
1.329
1.243
1.260
1.274
1.279
1.294
1.310
1.241
1.258
1.275
1.281
1.301
1.333
1.244
1.260
1.275
1.282
1.297
1.320
1.231
1.252
1.270
1.277
1.299
1.332
1.233
1.251
1.267
1.270
1.293
1.3
1.367
1.335
1.314
1.310
1.291
1.271
1.388
1.339
1.316
1.314
1.294
1.289
1.369
1.339
1.317
1.311
1.292
1.276
1.371
1.341
1.319
1.314
1.296
1.281
1.367
1.334
1.310
1.304
1.287
1.270
1.365
1.333
1.314
1.305
1.294
1.2
176.3
176.5
179.5
178.8
179.6
177.7
176.3
176.4
176.8
177.2
177.4
178.5
176.4
176.1
176.0
176.2
176.1
176.5
176.8
177.6
177.5
177.9
177.9
179.8
176.0
175.6
176.4
176.5
176.8
176.6
175.1
174.0
174.8
175.8
176.5
17
176.9
176.8
176.0
175.7
175.6
176.5
177.0
176.7
176.5
176.3
176.2
176.4
176.8
177.2
177.3
177.2
177.4
177.1
176.5
176.2
176.2
176.0
175.9
179.9
177.3
177.4
176.7
176.6
176.3
176.3
177.6
177.9
177.4
177.1
176.6
17
+
[
[
[
[
[
3-H]
3-H] (LS)
3-H] (HS)
4.83
8.65
8.75
12.28
16.37
2
+
0
0.10
2
+
3
+
3-H]
3-H]4+(LS)
4
4
4
4
4
4
5
5
5
5
5
5
6
6
6
6
6
6
7
7
7
7
7
7
8
8
8
8
8
8
+
4.53
8.10
8.25
11.59
15.18
2
2
3
+
(LS)
(HS)
0
0.15
+
+
4+(LS)
+
4.63
8.41
8.46
12.01
15.95
2
2
3
+
+
+
(LS)
(HS)
0
0.05
4+(LS)
+
4.34
7.86
8.00
11.30
14.89
2
2
3
+
+
+
(LS)
(HS)
0
0.14
4+(LS)
+
6.48
10.74
10.73
14.53
18.71
2
2
3
+
+
+
(LS)
(HS)
0
-0.01
4+(LS)
+
5.95
9.81
9.95
13.36
1
2
2
3
+
+
+
(LS)
(HS)
0
0.13
4+(LS)
a
b
Bonds lengths and bond angles are given for half of the molecule. Similar values are computed for the other half. For low- (LS) and high-spin
c
+
(
HS) states. IP ) E(model ) - E(model).
Scheme 3
1ag (out-of-phase and in-phase combinations of the d-type FMO
σ2) under C2h symmetry.
For the neutral species 3-H, the bonding between the metallic
and the carbon fragments is mainly governed by strong σ-type
interactions occurring between the high-lying metallic FMOs
3
bu and 3ag and the low-lying C4 orbitals 1bu and 2ag which
lead to an important electron donation from the C4 spacer toward
the metallic fragment. The degree of electron donation is
illustrated numerically by the braced digits in Figure 8 which
indicate the electron occupation of FMOs following the interac-
tion of the component fragments. The σ-type M-C bonding is
complemented by a rather weak π-type back-donation from
occupied metallic FMOs into the high-lying acceptor C4 FMOs
1au and 2bu. The electron occupation of these orbitals is
calculated to be 0.20 and 0.22, respectively. The large energy
difference between the donor metallic FMOs and the acceptor
orbitals on the C4 fragments limits the degree to which these
back-bonding interactions may contribute to the M-C bonding
in 3-H and related compounds. The predominant M-C π-type
interactions are actually filled/filled interactions between the
occupied carbon and metal π orbitals, in particular between the
1bg and 1ag FMOs of the C4 bridge and the corresponding
occupied metallic FMOs with the same symmetry (1bg and 2ag).
As a result of these interactions, the C4 orbitals are stabilized,
while the metallic orbitals are destabilized and become the
are consistent with the octet rule. The (C4)2- moiety gives rise
to sixteen MOs, six of which (two vacant and four occupied
for the formal charge considered) may interact with the metallic
fragment. These six FMOs, which are designated 1au and 2bu
(π*), 2ag (σ), 1bg and 1ag (π), and 1bu (σ) under C2h symmetry,
are schematically sketched on the right-hand side of Figure 8.
Each Ru(PH3)2Cp metal fragment is a typical pseudo-ML5 entity
presenting a radial hybrid orbital (σ1) situated above a “t2g” set
of d-type orbitals (π1, π2, σ2) (see Scheme 3).36 Consequently,
the binuclear ruthenium fragment exhibits a set of eight FMOs
which span 3bu and 3ag (out-of-phase and in-phase combinations
of the hybrid FMO σ1), 2bu and 2ag (out-of-phase and in-phase
combinations of the d-type FMO π1), 1au and 1bg (out-of-phase
and in-phase combinations of the d-type FMO π2), and 1bu and
37
(
36) Schilling, B. E. R.; Hoffmann, R.; Lichtenberger, D. L. J. Am. Chem.
(37) Lichtenberger, D. L.; Renshaw, S. K.; Wong, A.; Tagge, C. D.
Organometallics 1993, 12, 3522.
Soc. 1979, 101, 585.

Metal-Bonded C4 Chains
J. Am. Chem. Soc., Vol. 122, No. 9, 2000 1957
Cs model 3-H quite satisfactorily mimics the atomic distances
of the crystallographically characterized complex {Cp(PPh3)2-
Ru}2(µ-CtCCtC), 3-Ph. The computed Ru-C(R), C(R)-
C(â), and C(â)-C(â′) distances for 3-H are 0.030 Å longer,
0.016 Å longer, and 0.010 Å shorter than observed for the trans-
isomer of 3-Ph, which is the most accurately characterized
2
6
rotamer to date. The small deviations of the computed
distances from the experimental values may be ascribed to some
extent by the partial optimization and the different substituents,
PH3 in 3-H vs. PPh3 in 3-Ph. The computed Ru-C(R)-C(â)
and C(R)-C(â)-C(â′) angles (176.3 and 176.9°) are reproduced
at remarkably high accuracy with deviations of 1.3 and 0.1°,
respectively, from the experimental values. The good agreement
between metric parameters computed for 3-H and the corre-
sponding experimental values obtained from 3-Ph gives con-
n+
fidence in the computed bond distances in [3-H] cations for
which no X-ray data are available yet.
As expected from the qualitative EH approach discussed
n+
above, the atomic distances in the Ru-C4-Ru chain of [3-H]
were found to vary following the sequential removal of electrons
+
(
Table 4). For instance, upon oxidation of 3-H to [3-H]2 the
Ru-C(R) and C(â)-C(â′) bonds contract by 0.099 (5%) and
.053 Å (4%), respectively, whereas the C(R)-C(â) bond
lengthens by 0.035 Å (3%). Similarly, upon oxidation from
0
2+
4+
[
3-H] to [3-H] the Ru-C(R) and C(â)-C(â′) bonds shorten
by a further 0.070 (4%) and 0.043 Å (3%), respectively, while
the C(R)-C(â) bond lengthens by 0.053 Å (4%). Larger changes
in Re-C and C-C bond lengths were computed between the
rhenium analogues {Cp*(PPh3)(NO)Re}2(µ-C4) and [{Cp*-
(PPh3)(NO)Re}2(µ-C4)] . Nevertheless the changes in the
bond lengths computed as the oxidation of 3-H proceeds seem
to indicate a conversion of the neutral diyndiyl model complex
Figure 8. EH orbital interaction diagram for the neutral model complex
2
+ 15
[{Cp(PH
3
)
2
Ru}
2
(µ-C
4
)] (3-H) of C2h symmetry (labels in the C
s
symmetry group in parentheses). FMO occupations after interaction
are given in brackets.
3
-H (Figure 6, structure A) through the dicarbenic species
HOMOs of the neutral system. An important consequence of
these π-type interactions is the mixing of the C4 and Ru2 FMOs
which leads to a large percentage contribution from the carbon
atoms of the C4 unit to the HOMOs of 3-H (53% ruthenium
and 32% C4, and 64% ruthenium and 29% C4 in character for
2+
[3-H] (Figure 6, structure C) into an acetylene-bridged
4+
dicarbyne complex [3-H] (Figure 6, structure E). For illustra-
tion, the computed Ru-C bond length in [3-H] (1.85 Å) is
somewhat longer than OstC separations (ca 1.78 Å) observed
in osmium-carbyne complexes (no RutC distances have been
structurally determined at present). The gradual decrease in
4+
1bg and 2ag, respectively). The HOMOs are therefore delocalized
38
over the entire six-atom Ru-C4-Ru chain, and it may be
concluded that any oxidation process which involves loss of
electrons from these orbitals will not be exclusively metal-
centered. Since the HOMOs are antibonding between Ru and
C(R) and between C(â) and C(â′), but bonding between C(R)
and C(â), the computational work suggests that shortening of
the M-C and C-C single bonds and lengthening of the CtC
triple bonds are to be expected upon oxidation of 3-H.
In addition, it should be noted that the HOMOs are well
separated from the high-lying LUMOs 2au and 3bu (3.37 eV)
and are also removed from the other occupied metallic MOs,
as illustrated in the middle of Figure 8. Therefore 3-H should
be capable of losing up to four electrons and give rise to a series
of five oxidation states, as was observed experimentally for 3-Ph
and 3-Me.
bond order along the carbon chain is consistent with the bond
stretching frequencies [ν(CC)] measured experimentally (Table
1
, Figure 6). In addition, it is noteworthy that C-C distances
3+
computed for [3-H] compare rather well with the correspond-
ing C-C distances determined experimentally for the tricationic
diiron species [{Cp*(dippe)Fe}2(µ-C4)] .
3+ 23
One of the puzzling features associated with the spectral data
2+
2+
for [3-Ph] and [3-Me] lies in the apparent cumulenic
structure of the carbon chain, which, as has been indicated
above, is more in keeping with the nature of the rhenium
2+
2+
complex 3 than of the iron analogue 2 . On the basis of the
M o¨ ssbauer spectroscopic data, a high-spin diacetylenic diradical
+•
•+
2+
Fe-CtC-CtC-Fe valence formulation for 2 with
20
Fe(III) termini has been proposed. In an effort to address this
issue, spin-unrestricted calculations were carried out on the
model complex [3-H] . The results indicated no significant
These qualitative conclusions are supported further by density
functional molecular-orbital calculations, which were carried
2+
differences between the bond lengths optimized for the high-
spin (HS) and low-spin (LS) configurations. The largest
deviation was found in the Ru-C(R) separation, which is 0.008
Å longer in the LS configuration than in the HS configuration.
Comparable results were obtained from both HS and LS
configurations of the doubly charged diiron model compound
n+
out on the model complexes [3-H] (n ) 0-4). Partial density
n+
functional optimization on [3-H] was made under the Cs
symmetry constraint in order to reduce computational effort.
C symmetry (with the σh plane bisecting the Cp ligands and
s
containing the Ru-C4-Ru chain) instead of C2h symmetry was
chosen for the models in order to differentiate the ruthenium
centers.
(38) (a) Clark, G. R.; Marsden, K.; Roper, W. R.; Wright, L. J. J. Am.
Chem. Soc. 1980, 102, 6570. (b) Clark, G. R.; Edmonds, N. R.; Pauptit, R.
A.; Roper, W. R.; Waters, J. M.; Wright, A. H. J. Organomet. Chem. 1983,
244, C57.
Bond Distances. Pertinent results of DF geometry optimiza-
n+
tion on [3-H] (n ) 0-4) species are shown in Table 4. The

1958 J. Am. Chem. Soc., Vol. 122, No. 9, 2000
Bruce et al.
Table 5. Energies (ꢀ, eV) and Metal and C
4
Percentage Compositions of Selected Orbitals in the HOMO/LUMO Region of
MO
n+
n+
[
{Cp(PH
3
)
2
Ru}
2
(µ-C )] , [3-H] (n ) 0-4)
4
23a′′
36a′
22a′′
35a′
21a′′
34a′
33a′
32a′
[3-H]
ꢀ
occ
M
-1.18
0
42
-1.22
0
16
-3.00
2
27
-3.20
2
25
-4.35
2
59
-4.50
2
67
-4.61
2
63
-4.83
2
74
C
4
0
35
33
0
2
82
-4.02
-4.00
0/0
14/14
2/2
59
8
5
-6.85
-6.48
1/0
32/32
52/52
9/9
69
2
4
-6.89
-6.81
1/1
34/34
61/61
2/2
15
15
11
11
14
7
-7.93
-7.87
1/1
63/63
9/9
20/20
8/8
7
20
9
11
7
8
-8.35
-8.28
1/1
78/78
11/11
5/5
Cp
PH
ꢀ R)
(â)
(
3
)
2
[
3-H]+
-4.37
-4.32
0/0
41/41
0/0
27/27
32/32
-7.63
0
-8.04
-7.86
1/1
56/56
15/15
18/18
11/11
-11.59
2
-7.99
-7.92
1/1
61/61
6/6
23/23
10/10
-11.37
2
ꢀ
occ(R/â)
M(R/â)
C (R/â)
4
Cp(R/â)
4/4
(PH
3
)
2
(R/â)
79/79
-7.18
0
6/6
-10.30
0
3/3
-10.44
2
7/7
-11.91
2
[
3-H]2+(LS)
3-H]2 (HS)
ꢀ
occ
M
-11.36
2
55
40
31
36
38
46
54
77
C
4
0
28
32
37
23
9
44
12
8
56
3
3
-10.92
-10.40
1/0
38/38
57/56
3/3
15
25
14
10
25
10
7
28
11
11
5
6
-12.20
-11.93
1/1
77/76
12/12
5/6
Cp
PH
ꢀ(R)
(â)
(
3
)
2
+
[
-7.68
-7.57
0/0
40/40
0
28/28
32/32
-11.00
-10.95
0/0
38/38
0/0
28/28
33/33
-14.73
0
13
76
-7.48
-7.19
0/0
28/28
41/41
21/21
10/10
-11.15
-10.80
0/0
19/19
62/63
13/13
5/5
-10.48
-10.07
1/0
37/37
44/44
11/11
8/8
-13.93
-13.85
0/0
37/37
39/39
14/14
10/10
-17.44
0
-11.67
-11.45
1/1
48/48
16/16
23/23
13/13
-15.18
-15.15
1/1
33/33
15/15
34/34
17/17
-19.66
2
-11.42
-11.29
1/1
57/57
8/8
25/25
10/9
-14.83
-14.77
1/1
49/49
8/8
32/32
11/11
-18.23
2
42
7
-11.43
-11.30
1/1
57/56
6/6
26/27
10/10
-14.85
-14.78
1/1
49/49
8/8
32/32
11/11
-18.26
2
43
10
ꢀ
occ(R/â)
M(R/â)
C (R/â)
4
Cp(R/â)
PH (R/â)
ꢀ(R)
(â)
(
3
)
2
3/3
6/6
[
3-H]3
+
-14.46
-14.03
1/0
39/39
56/55
3/3
2/2
-18.04
0
-15.78
-15.59
1/1
73/73
12/12
7/8
7/6
-19.41
2
ꢀ
occ(R/â)
M(R/â)
C (R/â)
4
Cp(R/â)
(PH
3
)
2
(R/â)
3-H]4 (LS)
+
ꢀ
-14.98
0
13
79
[
occ
Μ
35
35
41
52
21
14
64
10
C
4
Cp
PH
7
3
6
1
18
12
5
2
43
21
38
12
35
12
17
8
(
3
)
2
2
+
[
[
{Cp(PH3)2Fe}2(µ-C4)] , which was used to mimic the complex
{Cp*(dppe)Fe}2(µ-C4)]2+ (2 ). Clearly, some care must be
2+
39
taken in assigning cumulenic or acetylenic forms to complexes
2
+
such as [3-H] on the basis of bond lengths alone.
MO Analysis. The density-functional molecular orbital
diagram of the neutral model 3-H shown in Figure 9 is
qualitatively similar to the EHMO diagram given in Figure 8.
A large energy gap separates the occupied and vacant orbital
sets (1.78 eV), as expected for complexes containing 18-electron
metal centers. It is informative to look at the energy and
composition of the orbitals located in the HOMO region in order
to better discuss the structural trends observed for 3-H upon
oxidation. To this end, a Mulliken atomic orbital population
analysis for selected MOs is given in Table 5. The 22′′ and
3
5a′ orbitals, which are the HOMOs for the neutral species 3-H,
Figure 9. DF orbital diagrams for the neutral model complexes {Cp-
are delocalized along the Ru-C4-Ru chain and feature an
appreciable component from C4 moiety. The 22a′′ level is 27%
metal and 59% C4 in character, whereas the 35a′ orbital contains
(
(
{
PH
µ-C
Cp*(CO)
3
)
4
2
Ru}
) (5), [{Cp*(dHpe)Ru}
Ru} (µ-C ) (8) of C
2
(µ-C
4
) (3-H), {Cp*(PH
(µ-C
symmetry. The metal/carbon percentage
3
)
2
Ru}
2
(µ-C
4
) (4), {Cp(dHpe)Ru}
2
-
2
4
) (6), {Cp(CO)
2
Ru} (µ-C ) (7), and
2
4
2
2
4
s
2
5% metal and 69% C4 character. The contour plots of the
contributions to HOMOs are given in parentheses.
HOMOs are illustrated in Figure 10 and confirm the EH results
discussed above; i.e., these MOs are π-type in character and
antibonding between Ru and C(R) and C(â) and C(â′) and
bonding between C(R) and C(â). They extend perpendicularly
to each other. The composition of these orbitals is not
significantly altered upon oxidation, and they remain essentially
delocalized over the six-atom Ru2C4 core, although there is a
small increase in the amount of metal character and a corre-
sponding decrease in the C4 content during the progression from
4
+
(39) Costuas, K.; Halet, J.-F.; Lapinte, C. Unpublished results, 1999.
3-H to [3-H] (Table 5). Thus, the bond length variations

Metal-Bonded C4 Chains
J. Am. Chem. Soc., Vol. 122, No. 9, 2000 1959
Table 6. Averaged Computed Hirshfeld Charges of Selected
n+
Atoms in the Complex Models [{Cp(PH
3
)
2
Ru}
2
(µ-C
2
4
)] , [3-H]n+,
n+
n+
n+
n+
n+
n+
[
[
[
{Cp*(PH
{Cp*(dHpe)Ru}
{Cp*(CO)
3
)
2
Ru}
2
(µ-C
(µ-C
(µ-C
)]n+, 8 (n ) 0-4)
4
)] , 4 , [{Cp(dHpe)Ru}
4
(µ-C )] , 5 ,
n+
n+
2
4
)] , 6 , [{Cp(CO)
2
Ru}
2
(µ-C
4
)] , 7 , and
n+
2
Ru}
2
4
n charge
0
1
2a
3
4a
Ru
3
4
5
6
7
8
-H
-H
-H
0.157
0.165
0.158
0.170
0.336
0.342
0.189
0.197
0.191
0.201
0.362
0.365
0.234
0.236
0.235
0.241
0.406
0.401
0.282
0.279
0.281
0.281
0.449
0.434
0.332
0.321
0.331
0.324
0.499
C(R)
3
4
5
6
7
8
-0.239
-0.230
-0.241
-0.232
-0.207
-0.201
-0.169
-0.168
-0.172
-0.171
-0.105
-0.111
-0.121
-0.127
-0.126
-0.132
-0.049
-0.068
-0.068
-0.081
-0.069
-0.083
0.018
-0.021
-0.048
-0.024
-0.046
0.070
-0.011
C(â)
3
4
5
6
7
8
-0.140
-0.137
-0.142
-0.139
-0.097
-0.099
-0.080
-0.083
-0.083
-0.086
-0.020
-0.030
-0.030
-0.039
-0.034
-0.043
0.036
0.024
0.007
0.021
0.004
0.095
0.064
0.075
0.041
0.071
0.044
0.146
Figure 10. Contour plots of (a) the 22a′′ MO (in the plane bisecting
the Cp ligands) and (b) the 35a′ MO [in a plane perpendicular to that
in (a)] HOMOs of the neutral model complex {Cp(PH
3
2
) Ru}
2
(µ-C
4
)
(
(
3-H). Contour values are (0.01, (0.02, (0.05, (0.1, (0.2, and (0.5
3
1/2
0.016
e/bohr )
.
a
Low-spin configuration.
computed upon oxidation (Table 4) are in agreement with the
notion of removal of electrons from these MOs. As both 22a′′
and 35a′ MOs have the same bonding/antibonding character
along the Ru-C4-Ru chain, it is not surprising that the Ru-C
and C-C bond lengths computed for the model complex
the HOMOs of the complex featuring the more electron-rich
iron termini due to an increase in the interactions between the
filled metal fragment and carbon-chain π-type orbitals similar
to those described above for 3-H. Interestingly enough, HOMOs
computed for the model complex {Cp(PH3)2Fe}2(µ-C4) are
much more metallic in nature than their corresponding MOs in
complex 3-H (38% and 33% vs 27% and 25% in MO 22a′′ and
3-H]2 are essentially identical for either the LS (35a′) (22a′′)
+
2
0
[
1
1
or HS (35a′) (22a′′) electronic configurations (Table 4).
Furthermore, regardless of the charge on the model complex
39
MO 35a′, respectively) which presumably contributes to the
n+
[
3-H] , the two 35a′ and 22a′′ MOs remain largely separated
metal-centered diradical character of the dioxidized complex
in energy from the higher vacant MOs and are also separated,
to a lesser extent, from the low-lying occupied MOs which are
mainly metallic in character (Table 5). The evolution of the
atomic net charges computed in the different models [{Cp(PH3)2-
2+
2
. Concomitantly, the participation of the C4 chain is smaller
in the former than in the latter (51% and 61% vs 59% and 69%
39
in MO 22a′′ and MO 35a′, respectively). Consequently, the
iron atoms are slightly negatively charged, whereas the ruthe-
nium atoms are slightly positively charged, and the carbon atoms
of the C4 chain are slightly less electron-rich in the iron species
n+
40,41
Ru}2(µ-C4)] according to the Hirshfeld analysis
confirms
the delocalized character of the 35a′ and 22a′′ MOs, and both
metal and carbon atoms lose electron density upon oxidation
than in the ruthenium species. Furthermore, in contrast to
(Table 6).
2+
[
3-H] similar energies are computed for both HS and LS
In accord with the diamagnetism observed for the dicationic
2+
configurations for the iron model [2-H] in accord with the
very weak antiferromagnetic coupling observed for 2 at low
temperature.
ficiently small to render 2 paramagnetic at liquid nitrogen
temperature.
2+
ruthenium species [3-Ph] , the singlet state associated with
2+
2
0
2+
the (35a′) (22a′′) electronic configuration of [3-H] is preferred
20,39
The singlet-triplet energy difference is suf-
by 0.1 eV (9.6 kJ/mol) over the triplet state which is associated
2+
1
1
with the (35a′) (22a′′) electronic configuration for the same
20
2
model complex. The singlet state associated with the (21a′′) -
35a′) electronic configuration is largely energetically favored
compared to the triplet state associated with the (21a′′) (35a′)
electronic configuration for the tetracationic species [3-H] .
With respect to the iron-based analogues such as 2, it should
also be noted that on the basis of CV evidence it has been
concluded that the iron-iron interaction across the C4 bridge
becomes greater as the electron density on the metal centers
increases.23 This observation may be taken as a qualitative
indication of an increase in the amount of carbon character in
Electronic Influence of the Surrounding Ligands. To
estimate the change in the electronic structure of 3-H induced
by various modifications of the donor/acceptor properties
associated with the surrounding ligands, DF calculations were
carried out on different models in which the Cp and PH3 ligands
of 3-H were substituted by Cp* and CO or PH2CH2CH2PH2
0
(
1
1
4
+
(dHpe), respectively. Selected structural parameters resulting
from the geometry optimizations of the complexes [{Cp*(PH3)2-
n+
n+
n+
n+
Ru}2(µ-C4)] , 4 , [{Cp(dHpe)Ru}2(µ-C4)] , 5 , [{Cp*-
n+
n+
n+
n+
(
dHpe)Ru}2(µ-C4)] , 6 , [{Cp(CO)2Ru}2(µ-C4)] , 7 , and
n+
n+
(40) In contrast to the Mulliken population analysis, the Hirschfeld
[{Cp*(CO)2Ru}2(µ-C4)] , 8 (n ) 0-4), are compared in
Table 4. It can be seen that for a given oxidation state, the
carbon-carbon separations are not significantly altered by
variation in the metal-ligand composition. We simply note a
very small contraction of the C(R)-C(â) contact (ca. 0.01 Å)
method yields atomic charges which are essentially stable against basis sets
variations and correctly reflect the electronegativity differences between
the atoms. See for example: Bickelhaupt, F. M.; van Eikama Hommes, N.
J. S.; Guerra, C. F.; Baerends, E. J. Organometallics 1996, 15, 2923.
(41) Hirshfeld, F. L. Theor. Chem. 1977, 44, 129.

1960 J. Am. Chem. Soc., Vol. 122, No. 9, 2000
Bruce et al.
in the carbonyl complexes 7n+ and 8n+ with respect to those
bearing phosphine ligands. In all cases there is the by now
familiar expansion of the C(R)-C(â) bonds and contraction of
the C(â)-C(â′) bonds upon oxidation.
The most significant variation in structural parameters in this
series of complexes occurs in the Ru-C(R) distances (Table
4
). The replacement of the weak π-acceptor phosphine ligands
n+
n+
by the strong π-acceptor carbonyl ligands in 7 and 8 and
consequent reduction in electron density at the metal centers
leads to a further decrease in the back-bonding interactions that
occur from the stabilized dπ manifolds of the metal atoms into
the π* FMOs of the C4 chain, resulting in the longer metal-
carbon separations. However, regardless of the surrounding
ligands tethered to the metal atoms, the singlet state electronic
configuration is slightly energetically favored over the triplet
state electronic configuration in the case of the dicationic species
(
Table 4), and cumulenic structures may be anticipated for each
2
+
2+
2+
2+
2+
of 4 , 5 , 6 , 7 , and 8 . Similar energies are computed
Figure 11. Successive ionization potentials (IP) computed for models
for model 72 with HS and LS configurations.
+
3
2
2
4
3
2
2
4
{Cp(PH
potentials (E°) measured for {Cp(PPh
Cp*(dippe)Fe} (µ-C ), respectively.
)
Ru}
(µ-C
) (3-H) and {Cp(PH
)
3
Fe}
(µ-C
) (2-H) vs redox
) (3-Ph) and
)
2
Ru}
2
(µ-C
4
The molecular orbital compositions and energy levels of the
neutral model complexes as a function of the metal-ligand
fragments are illustrated in Figure 9. Model complexes 4-6
exhibit electronic properties remarkably similar to those of
complex 3-H. The energy level schemes associated with these
compounds are practically identical, with the HOMOs of a′ and
a′′ symmetry separated from both the high-lying LUMOs and,
to a lesser extent, from the low-lying metal-based occupied
MOs. In contrast to the limited changes observed upon sub-
sitution of Cp for Cp*, or PH3 for dHpe, a more significant
effect is observed when the phosphine ligands PH3 or dHpe
are replaced by carbonyl ligands. In particular, an important
shift to lower energy is computed for MOs in the carbonyl
compounds 7 and 8. Nevertheless, their orbital schemes are
qualitatively similar to those for models containing phosphine
ligands with HOMOs lying in the middle of an energy gap
separating high-lying antibonding MOs from low-lying metal-
based nonbonding MOs (Figure 9). HOMO/LUMO gaps are
similar in all models (ca. 1.7 eV). As a result of the π-acceptor
character of the carbonyl ligand in 7 and 8, the metal-to-carbon
chain π-type back-bonding contribution to the HOMOs in these
complexes is reduced. Consequently, a comparison of the metal
vs carbon percentage contribution to the HOMOs reveals that
the replacement of phosphine ligands by carbonyl groups yields
HOMOs more heavily weighted on the carbon bridge. This
reflects in Hirshfeld atomic charges which indicate that electron
density loss of the carbon atoms upon oxidation is more
important in models 7 and 8 than in models bearing phosphine
groups (Table 6).
{
2
4
potentials by adding the differences between the solvation
energies of the reduced and oxidized species to the IPs of the
reduced species and correcting for the potential of the reference
1
9
electrode. A plot of IPs computed for 3-H vs oxidation
potentials experimentally measured for 3-Ph shows a linear
correlation (Figure 11). Assuming comparable solvation energies
n+
n+
for [3-H] and 6 , a plot of the IPs computed for 6 on this
curve indicates that successive oxidations of complexes contain-
ing electron-donating Cp* and diphosphine ligands should be
easier with a negative shift of ca. 0.15 V of the redox potentials
with respect to those measured for species 3-Ph. The increasing
ease of oxidation with strong electron-donating groups tethered
to the metal centers is in accord with the electrochemical results
showing that complex 3-Me is more readily oxidized than
complex 3-Ph (vide supra).
IPs are also dependent on the nature of the metal centers.
The first and second IPs computed for the iron model 2-H are
lower than the corresponding ones for 3-H. The third IP is nearly
similar in both models, whereas the fourth becomes larger in
39
2
-H with respect to 3-H. This is agreement with electrochemi-
cal data found for the iron and ruthenium compounds 2 and
2
0,23
3
.
The first and second oxidation waves occur at potentials
slightly less positive for species 2 with respect with species 3.
On the other hand, the third oxidation wave is observed at almost
the same potential for both compounds. The fourth oxidation
23
step has not yet been reported for the iron complexes. The
n+
plot of IPs computed for [2-H] vs experimental redox
Ionization Potentials. While experimental photoelectron
spectra have not yet been reported for the Ru2C4-based
n+
potentials of [{Cp*(dippe)Fe}2(µ-C4)] (Figure 11) suggests
that the fourth oxidation would occur over 2 V (vs SCE), a
value outside the potential windows of most solvents commonly
used for electrochemical studies.
molecules described in this work, the present calculations on
n+
[
3-H] (n ) 0-4) and the other related model complexes may
be used to predict the gas-phase ionization potentials (IP). The
n+
n+
adiabatic IPs computed for model complexes [3-H] and 4 -
Conclusion
n+
8
are compared in Table 4. They correspond to removal of
electrons housed in the HOMOs of a′ and a′′ symmetry. The
IPs are considerably lower in the case of complexes 3-H and
We have shown that the neutral complexes 3-Ph and 3-Me,
which contain a C4 chain end-capped by Ru(PR3)(PPh3)Cp (R
Ph or Me) moieties, can be oxidized to give a series of mono-,
di-, tri-, and tetracations. Theoretical calculations indicate that
oxidation of compounds 3 affects both the metal centers and
the carbon atoms of the C4 bridge, since this process corresponds
to the removal of electrons housed in MOs delocalized over all
atoms of the Ru-C4-Ru chain. Comparison of models with
different ligand surroundings suggests that molecules containing
4
-6, which contain phosphine ligands, than in the carbonyl
)
complexes 7 and 8. This indicates that the presence of strong
σ-donor ligands as surrounding ligands, i.e., rather electron-
rich metal centers, favor low IPs. The lowest IPs are computed
for model 6 which contains Cp* and dHpe, both electron-
donating groups.
In principle, redox potentials may be related to ionization

Metal-Bonded C4 Chains
J. Am. Chem. Soc., Vol. 122, No. 9, 2000 1961
5.03 (s, 5H, Cp). 13C NMR: δ 133.94-128.80 (m, Ph), 90.82 (s, Cp).
strong electron-donating ligands should be the more readily
oxidized.
2+
3 2 2 4
ES-MS (m/z): 715, [{Cp(PPh ) Ru} (C )] .
-
4
Mid-IR Spectra (IRRAS Cell). A solution of 1 (3-Ph, 7 × 10
-
4
M; 3-Me, 8 × 10 M) in CH
2
Cl
2
2
containing 0.1 M [NBu
4 6
]PF was
Experimental Section
7
introduced into the IRRAS cell and purged with dry N
2
. A thin film
(
ca. 20 µm) of sample solution was trapped between the Pt disk working
electrode (3 mm diameter), which was held at -0.22/-0.20 V (3-Ph/
-Me) with respect to a platinum wire pseudo-reference electrode, and
a CaF window through which the sample beam passed. A piece of Pt
gauze served as the counter electrode. The film was cooled to -40 to
General Experimental Conditions. All reactions were carried out
under dry, high-purity nitrogen unless otherwise stated, using standard
Schlenk techniques. Solvents were dried and distilled according to
convention. Elemental analyses were preformed by the Canadian
Microanalytical Service, Delta, BC, Canada.
3
2
-
+
50 °C prior to the spectroelectrochemical experiment. Oxidation at
0.22/+0.20, +0.72/+0.70, +1.45/+1.30, and +2.20/+1.70 V served
Instrumentation. IR spectra in Nujol were obtained from samples
mounted between NaCl disks with a Perkin-Elmer 1720X FT IR
+
2+
3+
4+
1
to generate the 3 , 3 , 3 , and 3 species, respectively. Difference
spectrometer. NMR spectra were recorded on Bruker ACP 300 ( H at
1
3
1
spectra were obtained by subtracting the spectrum of the precursor
3
00.13 MHz, C at 75.47 MHz) or Varian Gemini 200 ( H at 199.8
(
n-1)+
n+
1
3
3
complex from that of the 3 species being investigated.
MHz, C at 50.29 MHz) spectrometers. Samples were dissolved in
CDCl (Sigma). Electrospray mass spectra (ES MS) were obtained from
Reversibility was verified by reduction at a potential 0.20 V lower than
that used during the oxidation step, and regeneration of the precursor.
Near-IR, Vis, and UV Spectra (OTTLE Cell). Solutions of 3
3
samples dissolved in MeOH unless otherwise indicated. Solutions were
injected into a VG Platform II spectrometer via a 10 mL injection loop.
Nitrogen was used as the drying and nebulizing gas. Samples were
-
4
-3
(
[
3-Ph, 7 × 10 M; 3-Me, 2.8 × 10 M) in CH
2 2
Cl containing 0.5M
NBu ]BF were rigorously purged of dissolved oxygen by a passage
4
4
examined at cone voltages in the range 20-80 V to find the best
2
8
conditions. Chemical aids to ionization are indicated where used.42 The
2
of a stream of dry N then introduced to the OTTLE cell held at
IRRAS and OTTLE cells have been described in detail previously.2
7,28
-0.20/0.0 V (3-Ph/3-Me). A Pt gauze working electrode, Pt wire
counter electrode, and a Ag/AgCl reference electrode were employed.
The OTTLE cell was mounted in a cryostatic cell block and cooled to
The IRRAS spectra were collected on a Bio-Rad FTS 60A model
spectrometer from samples held at -50 °C, and OTTLE spectra from
the NIR to UV were collected on a Perkin-Elmer Lambda 9 spectrom-
-
+
30 °C by means of a stream of cold, dry nitrogen. Electrolysis at
+
2+
0.20/+0.20, +0.66/+0.60, and +1.32/+1.26 V gave the 3 , 3 , and
eter at -30 °C.
Reagents. {Cp(PPh
3+
3
species, respectively. Reversiblity was verified by the observation
) (3-Ph)24,26 and PMe
43
were
3
)
2
Ru}
2
(µ-C
4
3
of well-defined isosbestic points and the recovery of clean spectra
following electrolytic reduction.
Theoretical Calculations. Extended H u¨ ckel calculations were
prepared by the literature methods. AgPF
6
was purchased (Pennwalt)
and used as received. Solvents were dried and distilled prior to use
according to convention.
carried out on model {Cp(PH
3
)
2
Ru}
2
44
4
(µ-C ), 3-H, of C2h symmetry
Preparation of {Cp(PPh
was charged with 3-Ph (150 mg, 0.10 mmol), toluene (5 mL), and
PMe (110 µL, 1.2 mmol) and sealed under vacuum. The tube was
3 3 2 4
)(PMe )Ru} (µ-C ) (3-Me). A Carius tube
45
within the extended H u¨ ckel formalism using the program CACAO.
Standard atomic distances were taken. The exponents (ú) and the
valence shell ionization potentials (Hii in eV) were respectively the
following: 1.3, -13.6 for H 1s; 1.625, -21.4 for C 2s; 1.625, -11.4
for C 2p; 1.6, -18.6 for P 3s; 1.6, -14.0 for P 3p; 2.078, -8.6 for Ru
3
heated at 120 °C for 4 d to give a translucent orange solution. The
tube was opened, and the solvent was removed in vacuo. The oily
residue obtained was triturated with hexane under a N
-Me as an somewhat air-sensitive yellow powder (45 mg, 43%). Anal.
Found: C, 63.43; H 5.38. Calcd for C56 Ru : C, 63.64; H, 5.49.
IR (Nujol): ν(CtC) 1974 cm . H NMR: δ 7.70-7.15 (15H, m,
2
stream to give
5
s; 2.043, -5.1 for Ru 5p. The Hii value for Ru 4d was at -12.2. A
linear combination of two Slater-type orbitals with exponents ú ) 5.378
and ú ) 0.5340 and c
.6365 was used to represent the Ru 4d atomic orbitals.
3
1
H P
58 4
2
2
) 2.303 with the weighting coefficients c
1
2
)
-
1
1
0
1
3
Ph), 4.43 (5H, s, Cp), 1.17 (9H, br, PMe
3
). C NMR: δ 134.34-
Density functional calculations were carried out on models 3-H and
1
27.32 (m, Ph), 82.71 (s, Cp), 22.50 (br, PMe
3
). ES MS (m/z): 1058,
46
4
-10 using the Amsterdam density functional (ADF) program
+
+
+
M ; 796, [M - PPh
Preparation of [{Cp(PPh
rapidly stirred solution of 3-Ph (500 mg, 0.35 mmol) in CH
mL) was treated dropwise with a solution of AgPF (89 mg, 0.35 mmol)
3
] ; 505, [Ru(PMe
3
)(PPh
3
)Cp] .
47
developed by Baerends and co-workers. The Vosko-Wilk-Nusair
parametrization was used for the local density approximation (LDA)
with gradient corrections for exchange (Becke88) and correlation
3
2
) Ru}
2
(µ-C
4
)][PF
6
] ([3-Ph][PF
6
]). A
(50
48
2
Cl
2
49
6
(Perdew86).
50
s
C symmetry was chosen for the partially optimized
in 1,2-dimethoxyethane (10 mL). The resulting deep green solution
was filtered through a pad of Celite to remove the precipitated Ag metal,
and the solvent was removed from the filtrate. The residue was taken
models in order to differenciate the ruthenium centers. The geometry
optimization procedure was based on the method developed by Versluis
51
and Ziegler. The atom electronic configurations were described by a
up in a small volume of fresh CH
Et O. The resulting precipitate was collected, washed with Et
0 mL), and dried to give [3-Ph][PF ] (400 mg, 73%) as a forest-
green powder. Anal. Found: C, 65.45; H, 4.36. Calcd for C86
Ru : C, 65.52; H, 4.44. IR (Nujol): ν(CC) 1861, ν(PF) 861 cm . H
NMR: δ 7.3-7.1 (br, Ph), 5.0 (br, Cp). ES MS (m/z): 1430, [{Cp-
2
Cl
2
and filtered into rapidly stirred
O (3 ×
6
double-ú Slater-type orbital (STO) basis set for H 1s, C 2s and 2p, and
P 3s and 3p, augmented with a 3d single-ú polarization function for
the carbon atoms of the organic bridge. A triple-ú STO basis set was
used for Ru 4d and 5s, augmented with a single-ú 5p polarization
function. A frozen-core approximation was used to treat the core
2
2
1
70 6 5
H F P -
-
1 1
2
47
electrons of C, O, P, and Ru. Adiabatic ionization potentials were
+
+
(
PPh
Preparation of [{Cp(PPh
plex 3-Ph (500 mg, 0.35 mmol) in CH
a solution of AgPF (221 mg, 0.88 mmol) in 1,2-dimethoxyethane (20
3
)
2
Ru}
2
(C
4
)] ; 691, [Ru(PPh
3
)
2
Cp] .
(µ-C )][PF
Cl (50 mL) was treated with
defined as the energy difference between optimized geometries of the
reduced and oxidized species.
3
)
2
Ru}
2
4
6 2 6 2
] ([3-Ph][PF ] ). Com-
2
2
(43) Luetkens, M. F., Jr.; Sattelberger, A. P.; Murray, H. H.; Basil, J.
6
D.; Fackler, J. P. Inorg. Synth. 1989, 26, 7.
mL) in dropwise fashion. During the addition the color of the solution
changed from orange through deep green to dark blue. The solvent
was removed and the residue extracted with a small volume of fresh
(
44) Hoffmann, R. J. Chem. Phys. 1963, 39, 1397.
(45) Mealli, C.; Proserpio, D. J. Chem. Educ. 1990, 67, 399.
(46) Amsterdam Density Functional (ADF) Program, release 2.3; Vrije
CH
dark blue precipitate was crystallized (CH
PF as a dark blue microcrystalline solid. Anal. Found: C, 60.57;
H, 4.37. Calcd for C86 Ru : C, 60.07; H, 4.07. IR (Nujol): ν-
CC) 1766, ν(PF) 860 cm . H NMR: δ 7.70-7.07 (m, 30H, PPh );
2
Cl
2
. The extracts were filtered into stirred hexane, and the resulting
Universteit: Amsterdam, The Netherlands, 1997.
(
47) (a) Baerends, E. J.; Ellis, D. E.; Ros, P. Chem. Phys. 1973, 2, 41.
b) Baerends, E. J., Ros. P. Int. J. Quantum. Chem. 1978, S12, 169. (c)
Boerrigter, P. M.; te Velde, G.; Baerends, E. J. Int. J. Quantum Chem.
2
Cl /pentane) to give [3-Ph]-
2
(
[
6 2
]
H
70
F
12
P
6
2
1
988, 33, 87. (d) te Velde, G.; Baerends, E. J. J. Comput. Phys. 1992, 99,
-
1 1
(
3
84.
(
48) Vosko, S. H.; Wilk, L.; Nusair, M. Can. J. Phys. 1980, 58, 1200.
(
42) (a) Nicholson, B. K.; Henderson, W. J. Chem. Soc., Chem. Commun.
(49) Becke, A. D. Phys. ReV. 1988, A38, 3098.
1
995, 2531. (b) Henderson, W.; McIndoe, J. S.; Nicholson, B. K.; Dyson,
P. J. Chem. Commun. 1996, 1183. (c) Henderson, W.; McIndoe, J. S.;
Nicholson, B. K.; Dyson, P. J. J. Chem. Soc., Dalton Trans. 1998, 519.
(50) Perdew, J. P. Phys. ReV. 1986, B33, 8822; 1986, B34, 7406
(erratum).
(51) Verluis, L.; Ziegler, T. J. Chem. Phys. 1988, 88, 322.

1962 J. Am. Chem. Soc., Vol. 122, No. 9, 2000
Bruce et al.
Acknowledgment. Financial support of this work by the
computing facilities. We thank Prof. B. K. Nicholson (University
of Waikato, Hamilton, New Zealand) for the ES MS data.
Thanks are expressed to Prof. J.-Y. Saillard (Rennes, France)
and a reviewer for helpful comments.
Australian Research Council is gratefully acknowedged. P.J.L.
held an Australian Postgraduate Award. K.C. and J.-F.H. thank
the Centre de Ressources Informatiques (CRI) of Rennes and
the Institut de D e´ veloppement et de Ressources en Informatique
Scientifique (IDRIS-CNRS) of Orsay (Project 970649) for
JA992002T