Carbon-rich ruthenium complexes containing bis(allenylidene) and mixed alkynyl-allenylidene bridges

Article abstract of DOI:10.1002/ejic.200400457

Complexes cis-[RuCl(dppe)₂][X] (2a X = PF₆, 2b X = CF₃SO₃) react with a variety of bis(propargylic) alcohols to selectively lead to mono-frans-[Cl(dppe)₂Ru=C=C=C(R)-T-C(R)(OH)- (C≡C-H)][X] (4) [R = H, Ph; T = m,p-(C₆H₄), 2,5-(thiophene), 5,5′-(2,2′-bithiophene), 5,5″-(2,2′: 5′2″-terthiophene), -C≡C-] or bis(allenylidene) trans-[Cl(dppe)₂Ru=C=C=C(R)-T-(R)C= C=C=RuCl(dppe) ₂][X]₂ (5) complexes. New dimetallic and trimetallic complexes containing mixed alkynyl-allenylidene bridges, trans-[Cl(dppe) ₂Ru-C≡C-p-(C₆H₄)-(Ph)C=C=C= RuCl(dppe)₂][CF₃SO₃] (12) and trans-[{Cl(dppe)₂Ru-C≡C-p-(C₆H₄)} ₂C=C=C=RuCl(dppe)₂][CF₃SO₃] (17)}, were prepared by modification of the carbon-rich ligand of acetylide precursors. UV/Vis and cyclic voltammetry studies show the influence of the unsaturated conjugated bridge on the electronic interaction between the redox centers, and the fine tuning of this property. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005.

Full text of DOI:10.1002/ejic.200400457

FULL PAPER
Carbon-Rich Ruthenium Complexes Containing Bis(allenylidene) and Mixed
Alkynyl؊Allenylidene Bridges
[a]
[a]
[b]
[a]
´
Stephane Rigaut,* Johann Perruchon, Salaheddine Guesmi, Claire Fave,
Daniel Touchard,*[a] and Pierre H. Dixneuf[a]
Keywords: Allenylidene / Bridging ligands / Ruthenium / Redox systems / Alkynyl ligands
Complexes cis-[RuCl(dppe)2][X] (2a X = PF6, 2b X = CF3SO3)
react with a variety of bis(propargylic) alcohols to selectively
lead to mono-trans-[Cl(dppe)2Ru=C=C=C(R)−T−C(R)(OH)-
(CϵC−H)][X] (4) [R = H, Ph; T = m,p-(C6H4), 2,5-(thiophene),
RuCl(dppe)2][CF3SO3] (12) and trans-[{Cl(dppe)2Ru−CϵC−p-
(C6H4)}2C=C=C=RuCl(dppe)2][CF3SO3] (17)}, were prepared
by modification of the carbon-rich ligand of acetylide pre-
cursors. UV/Vis and cyclic voltammetry studies show the
5,5Ј-(2,2Ј-bithiophene), 5,5ЈЈ-(2,2Ј:5Ј2ЈЈ-terthiophene), −CϵC−] influence of the unsaturated conjugated bridge on the elec-
or bis(allenylidene) trans-[Cl(dppe)2Ru=C=C=C(R)−T−(R)C=
C=C=RuCl(dppe)2][X]2 (5) complexes. New dimetallic and
trimetallic complexes containing mixed alkynyl−allenylidene
tronic interaction between the redox centers, and the fine
tuning of this property.
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2005)
bridges,
trans-[Cl(dppe)2Ru−CϵC−p-(C6H4)−(Ph)C=C=C=
Introduction
CHϪCϵCϪRu(PPh3)2Cp]BF4.[10a] Highly conjugated mol-
ecules resulting from the coupling of an acetylide complex
with a vinylidene[8,9] or an allenylidene[6] complex are also
emerging examples.
Organometallic complexes with π-conjugated bridges
are attracting interest for their electronic and structural
properties in fields including liquid crystals,[1] nonlinear
Ruthenium systems[15] present opportunities for the syn-
thesis of novel organometallic compounds as models for
electron conduction, and with unusual and stable topolog-
optical
devices,[2]
luminescence,[3]
and
electronic
communication.[4Ϫ11] Electronic communication between
two functionalities is a fundamental aspect related to a vari-
ety of complex systems ranging from life[12] to photoactive
donor/acceptor processes[13] and electronic devices.[14]
These properties are usually the result of their linear rigid
structure and of their π-electron conjugation. Thus, it is
crucial to understand the behavior of such systems with
multiple redox components, the influence of the linkers, and
to develop straightforward methods of access to them.
Dimetallic complexes have been obtained by coupling of
organometallic terminal acetylides to bis(vinylidene) and
bis(alkynyl) complexes.[4,5] By contrast, few dimetallic
mixed alkynylϪvinylidene or alkynylϪallenylidene com-
plexes have been selectively synthesized by activation of
conjugated organic molecules.[10] For example, the acti-
vation of HCϵCϪCH(OH)ϪCϵCH has led to a dimetallic
system with a C5 bridging ligand [CpRu(PPh3)2ϭCϭCϭ
ies.[16,17] The ruthenium [RuCl2(dppe)2] (dppe
ϭ
Ph2PCH2CH2PPh2) species offers the possibility to easily
link two carbon-rich chains to form reversible redox sys-
tems[16,18] with an optical transition highly dependent on
the nature of the chain.[6,19] This fact gave us impetus to
build polynuclear systems containing new types of delo-
calized carbon-rich bridges and linking reversible redox ac-
tive moieties, especially allenylidenes. We now report the
easy synthesis of stable dimetallic complexes containing a
variety of new bis(allenylidene) bridges separated by a tun-
able conjugated linker and the synthesis of novel di- and
triruthenium compounds containing mixed allenylidene and
alkynyl groups. We further illustrate, in the light of UV/Vis
and electrochemical studies, the large influence of the
bridge on the electronic interaction between the redox cen-
ters.
[a]
´
Institut de Chimie de Rennes, UMR 6509 CNRS-Universite de
Results and Discussion
´
Rennes 1, Organometalliques et Catalyse,
Campus de Beaulieu, 35042 Rennes Cedex, France
Fax: (internat.) ϩ 33-2-2323-6939
The activation of terminal alkyne functionalities with the
sixteen-electron species [ClRu(dppe)2]ϩ can be potentially
employed to access polymetallic systems with carbon-rich
unsaturated bridges, as previously shown with the synthesis
E-mail: Daniel.touchard@univ-rennes1.fr
stephane.rigaut@univ-rennes1.fr
[b]
´
Laboratoire de Chimie de Coordination et Analytique, Faculte
´
des Sciences, Universite Chouaib Doukkali,
B. P. 20, El-Jadida, Morocco,
Eur. J. Inorg. Chem. 2005, 447Ϫ460
DOI: 10.1002/ejic.200400457
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S. Rigaut, J. Perruchon, S. Guesmi, C. Fave, D. Touchard, P. H. Dixneuf
FULL PAPER
of bis(vinylidene) and bis(acetylide) derivatives.[20] Herein, (41Ϫ81% yield) bearing a free propargylic alcohol group
we use the selective activation of a variety of functional (Scheme 1). These allenylidenes are stable with respect to
groups with the intent of forming carbon-rich allenylidene the addition of methanol to the Cα carbon.[26] The FTIR
ruthenium derivatives: (i) The simple or double activation spectra of the allenylidenes 4aϪh show characteristic fea-
of molecules containing two terminal propargylic alcohol tures for such compounds with νCϭCϭC ϭ 1921Ϫ1939 cmϪ1
functional groups, via the Selegue method,[21] offers access and νCϵC ϭ 2100Ϫ2200 cmϪ1. The 31P NMR spectra dis-
to mono(allenylidenes) or bis(allenylidenes).[22] (ii) New play the equivalence of the four phosphorus nuclei and thus
mixed terminal alkynylϪallenylidene functionalities sepa- the relative trans disposition of the chlorine atom and of
rated by a phenyl linker were achieved by using an original the allenylidene ligand. The characteristic allenylidene low-
step-by-step organometallic synthesis, i.e. by modification field 13C signal for the Cα carbon nucleus appears as a quin-
2
and activation of the organic carbon-rich ligand of mono- tuplet at δ ϭ 288Ϫ320 ppm with JP,C ϭ 15 Hz.
and dimetallic acetylides to introduce the conjugated alleny-
lidene function.
Synthesis of Bis(allenylidene)ruthenium Complexes: The
free prop-2-yn-1-ol functionality of complexes 4aϪh can be
It has to be noted that we described recently the pro- activated with 1 equiv. of 2a or 2b in dichloromethane, lead-
tonation of a ruthenium bis(allenylidene), obtained by ing to the slow formation of the bis(allenylidene) complexes
means of the Selegue strategy, into a bis(carbyne).[19] It is 5aϪh (7 d). The same bridged molecules were also readily
also noteworthy that Werner et al. obtained a similar bis(al- prepared by the assembly of 2 equiv. of 2a or 2b and 1
lenylidene) with rhodium [Cl(PiPr3)2RhϭCϭCϭC(Ph)Ϫm- equiv. of the corresponding bis(propargylic) alcohol and
C6H4Ϫ(Ph)CϭCϭCϭRh(PiPr3)2Cl] by an identical ap- isolated in 42Ϫ78% yield after stirring for 7 d (Scheme 1).
proach.[23] A different kind of bis(allenylidene) not connec- The tertiary allenylidenes 5cϪh are more stable than the
ted through the allenylidene functions such as (Ph2CϭCϭ secondary allenylidenes 5aϪb (see Scheme 1). Hence, our
CϭRh(PiPr3)2ϪCϵCϪ)2 was also synthesized by the same studies have been mainly focused on these former com-
group.[24] However, no electrochemical studies were re- plexes. For all complexes, the 31P NMR spectrum demon-
ported for these complexes.
strates the high symmetry of the molecule with only one
Synthesis of Mono(allenylidene)ruthenium Complexes: sharp singlet for the eight phosphorus nuclei. The two allen-
The reaction of the 16-electron salts 2a or 2b with an excess ylidene groups are then equivalent, and therefore the 13C
of bis(propargylic) alcohols[25] 3aϪh leads to the formation NMR spectra show only one set of three different signals
of red monoallenylidene ruthenium complexes 4aϪh for the Cα, Cβ and Cγ carbon atoms. However, complex 5h
Scheme 1
448
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Carbon-Rich Ruthenium Complexes
FULL PAPER
Scheme 2
with the triple bond is not stable enough in solution, and
Synthesis of (Alkynyl؊Allenylidene)ruthenium Complexes:
the 13C NMR spectrum could not be obtained. Finally, the The activation of terminal alkyne 8 or 13 bearing a ketone
attempt to obtain a trisallenylidene complex by triple acti- further convertible into a propargylic alcohol function with
vation of the propargylic alcohol 6 with 2b failed. Only the 2b, led to the mono- (9) and the bis(vinylidene) (14) com-
bis(allenylidene) complex 7 was recovered (Scheme 2), plexes in good yields (Scheme 3). The vinylidenes display
probably for steric reasons, as a trisallenylidene ruthenium characteristic FTIR vibration stretches νCϭC ϭ 1588 cmϪ1
complex was obtained when the propargylic alcohol func- and νCO ϭ 1640 cmϪ1. The 1H NMR spectra shows a quin-
tionalities were separated by a larger nonconjugated tri- tet for the vinylidene proton at δ ϭ 4.82 ppm for 9 and at
podal core.[27]
δ ϭ 4.74 ppm for the two identical vinylidene protons of 14
Scheme 3
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S. Rigaut, J. Perruchon, S. Guesmi, C. Fave, D. Touchard, P. H. Dixneuf
FULL PAPER
4
with JPH ϭ 3 Hz. The low-field 13C signal for the Cα car- for a diffusion controlled process, and the ratio of the peak
bon nucleus appears as a quintet at δ ϭ 352 ppm for 9 and currents (ipa/ipc) is close to unity. These electrochemical
354 ppm for 14, and a singlet at δ ϭ 195 ppm for the pen- studies show that the cationic monoallenylidenes 4cϪh can
dant ketone carbon nucleus is also observed. These vinyl- undergo a one-electron reduction, and the bis(allenylidenes)
idene complexes can be easily deprotonated with a base 5aϪh, 7, two consecutive one-electron reductions. The cy-
such as DBU to form the neutral alkynylϪruthenium de- clic voltammograms of complexes 4e and 5e are presented
rivatives 10 and 15. The alkynylϪruthenium complexes in Figure 1 for illustration. It is noteworthy that these ter-
show characteristic vibration stretches νCϵC ϭ 2057 for 10 tiary monoallenylidenes undergo one reversible process, in
and νCϵC ϭ 2053 for 15. The carbonyl group of these com- contrast to secondary allenylidene complexes, which present
plexes is further converted into a propargylic alcohol func- an irreversible process.[22] The electrochemical behavior of
tion by action of lithium acetylide to give 11 and 16. the bis(allenylidenes) show several interesting features: (i)
Characteristic FTIR vibration stretches are observed at the two reversible processes are well separated from each
νϵCϪH ϭ 3050, νCϵCH ϭ 2135, νCϵC ϭ 2065 cmϪ1 for 11 other, and (ii) a significant anodic shift of both reduction
and νϵCϪH ϭ 3052, νCϵCH ϭ 2136, νCϵC ϭ 2068 cmϪ1 for potentials indicates that the reductions are thermo-
16. Finally, the activation of these propargylic alcohol dynamically favored with respect to the mononuclear ana-
groups by the active 16-electron species 2b leads to the iso- log when the two allenylidene moieties are conjugated in
lation of the dimetallic mixed alkynylϪallenylidene 12 or 5aϪc, eϪh. For example the reduction of 4e occurs at E° ϭ
of the trimetallic complex 17 bearing two alkynyl and one Ϫ1.000 V vs. Fc, and reductions of the corresponding di-
allenylidene groups. The overall yields for complexes 12 and metallic complex 5e are observed at less negative potentials,
17 are 37 and 50% starting from 2b after four steps, and i.e. at E°1 ϭ Ϫ0.439 and E°2 ϭ Ϫ0.749 V vs. Fc. No such
they display two typical absorptions at 2040 and 1926 (12), anodic shift is observed in the nonconjugated complexes 5d
2008 and 1912 (17) cmϪ1. The 13C spectrum shows the pres- or 7, in which the allenylidene moieties are in a meta orien-
ence of the allenylidene group with characteristic reson- tation on the phenyl linker. Indeed, for 5d, the two re-
ances for 12 and 17 at δ ϭ 345 and 342 ppm respectively ductions occur at E°1 ϭ Ϫ0.877 and E°2 ϭ Ϫ1.056 V vs.
for Cα, and also of the acetylide group with δ ϭ 135 and Fc, while 4d shows a reduction wave at E° ϭ Ϫ0.910 V vs.
134 ppm for CαЈ.
Fc. When two different redox processes exist for two other-
Electrochemical and UV/Vis Studies: The bis(allenylidene) wise identical redox systems in the same molecule, an im-
complexes are composed of two one-electron redox-active portant parameter is the comproportionation constant Kc.
units and of a bridge that allows for electronic communi- The large wave separation observed for each dimetallic
cation. To understand the nature of the redox behavior and complex (∆E°
Ͼ 180 mV) leads to large compro-
the role of the linker, the cyclic voltammograms of 4 and 5 portionation constants [Kc Ͼ 1.0ϫ103; Ϫ(RT/F) ln(Kc) ϭ
were recorded in CH2Cl2 solutions (0.1 m Bu4NPF6). The ∆E°] and establishes that all the monoreduced species are
reduction potentials and other relevant data for all com- stable in solution with respect to disproportionation.[28]
pounds are reported in Table 1. All complexes exhibite a
It has already been mentioned that the reduction of allen-
linear dependence of the peak current on the square root ylidene complexes mainly involves the allenylidene
of the sweep rate (v1/2) from 60 to 600 mV·sϪ1, as expected ligands,[29Ϫ32] in contrast to the oxidation of neutral acetyl-
Table 1. Electrochemistry and optical data for complexes 4, 5 and 7
CV[a]
E°2 [V]
UV/Vis[b]
E°1 [V]
∆E
[mV]
∆E
[mV]
E°2 Ϫ E°1
[mV]
Kc
λmax.
ε [molϪ1·L·cmϪ1
]
(MLCT) [nm]
5a
5b
4c
5c
4d
5d
4e
5e
4f
Ϫ0.509
Ϫ0.335
Ϫ0.910
Ϫ0.500
Ϫ0.910
Ϫ0.877
Ϫ1.000
Ϫ0.439
Ϫ1.012
Ϫ0.434
Ϫ1.027
Ϫ0.427
Ϫ0.805
Ϫ0.285
Ϫ0.890
66
71
60
60
60
60
66
66
60
66
60
66
60
60
60
Ϫ0.711
Ϫ0.606
81
80
202
270
2.3 ϫ 103
3.2 ϫ 104
530
588
520
522
560
714
660
730
692
752
512
720
520
28000
54000
28000
36000
26400
86000
28000
48000
25000
65000
26000
60000
38000
Ϫ0.680
Ϫ1.056
Ϫ0.749
Ϫ0.746
Ϫ0.760
60
60
90
90
69
180
180
310
320
330
1.0 ϫ 103
1.0 ϫ 103
1.5 ϫ 105
2.2 ϫ 105
3.2 ϫ 105
5f
4g
5g
4h
5h
7
Ϫ0.645
Ϫ1.100
60
60
360
210
1.0 ϫ 106
3.2 ϫ 103
[a]
Sample 1 mm; Bu4NPF6[b(]0.1 m) in CH2Cl2; v ϭ 100 mV sϪ1; potentials are reported in V vs. ferrocene as an internal standard.
Reversible redox processes. In CH2Cl2.
450
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Carbon-Rich Ruthenium Complexes
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on the chain together with this metal participation give rise
to strongly overlapping resonance lines that cannot be re-
solved. However, this result suggests that the radical is
highly centered on the organic bridge and is stabilized by
delocalization along the carbon bridge between the ru-
thenium centers. Interestingly, further addition of co-
baltocene leads to the two-electron reduction and to the
disappearance of the signal, which suggest the formation of
a diamagnetic doubly reduced species. 31P NMR studies of
the latter, obtained with 2 equivalents of cobaltocene, show
a single signal with δ ϭ 49.3 ppm consistent with a di-
acetylide species 18 (Scheme 4), that corroborates the com-
munication through the bridge. Unfortunately, the spectra
were broad, certainly because of the presence of residual
paramagnetic compound (the reductant or first reduced
species), and no exploitable proton or carbon spectra could
be obtained.
Figure 1. Cyclic voltammetry for 4c (dashed) and 5c (solid);
Bu4NPF6 (0.1 m) in CH2Cl2; v ϭ 100 mV·sϪ1
ide, which occurs on the metal center.[33] Thus, the re-
duction processes of the mono- and the bis(allenylidene)
can be attributed to the reduction of the carbon-rich chain
in analogy to the mono(allenylidene) species trans-
[Cl(dppe)2RuϭCϭCϭCPh2]PF6
(A1)
and
trans-
[Cl(dppe)2RuϭCϭCϭCMe2]PF6 (A2). Nevertheless, this
IR studies, recorded in CH2Cl2, show the shift of the al-
attribution was verified for 4c and 5c with the p-phenyl lenylidene band upon reduction of 4c from 1925 cmϪ1 to a
linker. For complex 4c, the most appropriate reducing agent sharper but more intense band at 1948 cmϪ1, similar to that
is the cobaltocene [Cp2Co] (i) as its reduction potential E° observed for A1 (from 1926 to 1945 cmϪ1). This new value
is Ϫ1.33 V vs. ferrocene,[34] and (ii) it is ESR silent down to is somewhat different from that of true acetylide
temperatures considerably below that of liquid nitrogen.[34b] (2000 cmϪ1) but coherent with the increase of the acetylide
We generated the reduced form in situ by dropping a crystal character of the reduced complexes, and with the presence
of cobaltocene in a THF solution of 4c in a capped ESR of a delocalized electron mainly on the allenylidene carbon
tube. Reduced complex 4c showed an intense and persistent atoms of the chain (Scheme 4). Winter’s et al. observed
signal (g ϭ 2.0048) similar to that observed for A1 (g ϭ similar shifts for other reduced allenylidene complexes.[31]
2.0042), hence centered close to the free electron g value (a On the other hand, the first reduction of 5c leads to a small
in Figure 2). The complex pattern could best be rationalized opposite shift of the allenylidene band from 1912 to
by the coupling of the unpaired electron with the four phos- 1906 cmϪ1. This last band is similar to that found for trans-
phorus nuclei and further coupling with the ortho, meta and [Cl(dppe)2RuϪCϵCϪC(CH3)ϭC(H)ϪC(CH3)ϭCϭCϭ
para hydrogens of the phenyl groups, showing the delocali- Ru(dppe)2Cl]BF4 (C)[6] (1898 cmϪ1) and consistent with the
zation of the single electron on the carbon-rich bridge.[35a] presence of delocalized allenylidene and acetylide moieties
On the other hand, the first reduction of 5c with decame- on the same bridge; two possible mesomeric forms are rep-
thylferrocene (E° ϭ Ϫ0.590 V vs. ferrocene) or with a de- resented in Scheme 4. The second reduction leads to the
ficient amount of cobaltocene in the ESR cavity leads to vanishing of the former band, and to the concomitant for-
the observation of a broad signal with g ϭ 2.0244 (b in mation a weak absorption at 1988 cmϪ1 (Figure 3). This
Figure 2). The observed shoulders may indicate some tran- corroborates the formation of a diamagnetic bis(acetylide)
sition metal contribution (d-orbitals of the ruthenium species such as 18. It is noteworthy that all these obser-
atoms) resulting in the coupling of the free electron with the vations are not related to the decomposition of the reduced
99Ru and 101Ru isotopes (nuclear spin S ϭ 5/2, and natural species. Indeed, all reduced forms were thermally stable and
abundances of 12.7 and 17% respectively) with an estimated reductions followed by oxidations with ferrocenium salt
coupling constant of approximately 5 G.[35b] It is possible 30 min later led to the pure starting materials on the basis
that the large number of magnetically independent nuclei of 31P NMR spectroscopy. Hence, in conclusion to these
Figure 2. ESR spectra resulting from the reduction of (a) 4c (g ϭ 2.0048), and of (b) 5c (g ϭ 2.0244)
Eur. J. Inorg. Chem. 2005, 447Ϫ460
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S. Rigaut, J. Perruchon, S. Guesmi, C. Fave, D. Touchard, P. H. Dixneuf
FULL PAPER
Scheme 4
spectroscopic studies, it is likely that all the electrons issued gation will show the stronger variation for both reduction
from reduction processes reside in an orbital with a signifi- processes in comparison to analogous monometallic species
cant carbon-rich ligand character but also with a non-negli- (Figure 1). According to common belief, the difference in
gible metal contribution.[32]
electrochemical half-wave potential reflects the strength of
interaction between the allenylidene moieties. There are,
however, various additional factors that contribute to a sta-
bilization of symmetrical mono- and bireduced complexes
and especially electron delocalization. By contrast, when
two redox centers are isolated from each other, E1 and E2
would be expected to be not only the same or similar but
also very close to the potential of the comparable mononu-
clear analog.[36] The observed first and second reduction
potentials of bis(allenylidene) species such as 5c are less
negative than those of the corresponding mononuclear
species; this indicates considerable stabilization of the re-
duced forms by resonance and allows an analysis of the
relative stabilization effects. The variation in potential is
greater with less aromatic linkers (thiophene) relative to the
phenyl transmitter, and the most efficient group to effect
communication is the triple bond (5h). For example, this
effect was already observed with dimetallic iron acetylides
Figure 3. IR spectra of 5c (—), its first (---), and second (···) re-
duced species
[Cp*(dppe)FeϪCϵCϪRϪCϵCϪFe(dppe)Cp*]
(R
ϭ
Ϫ2,5-C4H2SϪ, Ϫm-C6H4Ϫ).[37] For the nonconjugated
complexes 5d or 7 (with E°1 ϭ Ϫ0.877 and Ϫ0.890 V vs. Fc
respectively) the first reduction potential is very close to
that of the monometallic species (E° ϭ Ϫ0.910 V vs. Fc for
4d) as the allenylide centers interact weakly. We also ob-
served that the separation between the two processes (∆E°)
also depends on the nature of the transmitter. The ∆E°
value of 180 mV (Kc ϭ 1.0 ϫ 103) is observed with the
nonconjugated systems 5d and 7. Surprisingly, the conju-
gated p-phenyl linker 5c displays the same value, in contrast
The dependence of redox potentials on the nature of the
carbon-rich-ligand (Table 1) complexes is consistent with
the ligand character of the LUMO. The reduction potential
within the set of monoallenylidene species is located be-
tween 0.805 V and 1.027 V vs. ferrocene. A lower potential,
that is, a higher electron stabilization along the chain is ob-
served for 4h with the triple bond as transmitter with E° ϭ
Ϫ0.805 V vs. Fc. Within the series of bis(allenylidene) spec-
ies, the variations of E° for both reductions are expected to
be much greater. The complexes with the improved conju-
452
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Carbon-Rich Ruthenium Complexes
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to the acetylide iron systems.[37] Kc assumes a value of 4 energy in the bis(allenylidene)s 5c, 5e, 5f, 5g and 5h is con-
when the two redox sites are completely noninteracting and sistent with a more effective conjugated path between the
goes to much higher values as electronic and electrostatic two organometallic moieties, and with a decreasing energy
interactions increase. Therefore, the present value is princi- of the LUMO, as observed in the electrochemical studies.
pally attributed to a structural rearrangement, solvation or Even though the tendency is the same in the UV/Vis studies,
electrostatic interactions. For the complexes 5a, 5b, 5e and in electrochemistry, some differences are observed. The en-
5h, this value is noticeably higher, and the greatest differ- ergy difference between the mono- and the bis(allenylidene)
ence is observed with 5h (∆E° ϭ 360 mV, Kc ϭ 1.0 ϫ 106). band (∆λ) follows the order: triple bond (∆λ ϭ 192 nm) Ͼ
We then assign this significant increase to an additional thiophene (∆λ ϭ 154 nm) Ͼ p-phenyl (∆λ ϭ58 nm), but
contribution from the resonance interaction between the al- with bithiophene (∆λ ϭ 70 nm) and terthiophene (∆λ ϭ
lenylidene moieties through the linkers. Thus, in addition to 60 nm) the difference is barely larger than that for the phe-
the largest anodic shift, the less aromatic linkers with the nyl group. This observation could be related to the well-
shorter pathways display the greater differences in potential known rotational disorder of oligothiophenes in the ground
between the reduction processes (5eϪh) in the following or- state and to the corresponding reorganization energy neces-
der: Triple bond Ͼ thiophene ഠ bithiophene ഠ terthio- sary in the excited state. In addition, an energy modification
phene Ͼ phenyl.
of the heavily metal-centered HOMOs arising from a lower
UV/Vis studies were performed to compare mono- and metal d-orbital contribution in complexes with more ex-
dimetallic complexes. Figure 4 shows the absorption spectra tended π-conjugated ligands cannot be excluded.[32,38,39] It
obtained for 4c and 5c. The intense short-wavelength ab- is noteworthy that the absorption bands are very broad, cer-
sorption band for the nϪπ* type transition originating from tainly including several transitions, and these conclusions
the dppe ligand at high energy remains unchanged. By con- need to be considered with care, even if similar trends were
trast, the lower-energy transition is shifted from λmax.
ϭ
already observed in acetylide systems.[5e]
530 nm for 4c to a broader band at λmax. ϭ 588 nm for 5c.
In conclusion, according to both UV/Vis and electro-
This phenomenon is consistent with the observation made chemical studies, an important contribution from a less aro-
for the bis(carbyne) complex trans-[Cl(dppe)2RuϵCϪHCϭ matic π-conjugated system undoubtedly increases the elec-
C(CH3)ϪC6H4Ϫ(CH3)CϭCHϪCϵRu(dppe)2Cl](BF4)2, tronic communication between the allenylidene moieties
which displays a broad band at λmax. ϭ 559 nm, whereas and stabilizes the LUMO of the bis(allenylidene) complexes,
the monometallic compound, trans-[Cl(dppe)2RuϵCϪ the orbital in which the electrons are injected upon re-
CHϭC(CH3)R](BF4)2, absorbs at λmax. ϭ 426 nm.[19] For duction. These results are consistent with the general result
monoallenylidenes, the transition is attributed to the al- that the separation between energy levels continually dimin-
lowed transition from the metal-based HOMO-1 to the ishes in π-conjugated systems with decreasing aromaticity.
LUMO which is delocalized over the allenylidene ligand
(the HOMO/LUMO symmetry is forbidden),[31] and ac- (17) acetylide moieties were also studied (Figure 5, Table 2).
counts for the strong Metal-to-Ligand Charge Transfer They both show a one-electron reduction wave at E°red
The cationic allenylidene complexes with one (12) or two
ϭ
(MLCT). Concerning the new broad band observed for the Ϫ1.170 and Ϫ1.240 V vs. Fc respectively, and 12 displays a
dimetallic species, an important MLCT character also one-electron oxidation wave at E°ox ϭ 0.140 V vs. Fc
seems to be present. This large bathochromic shift of the while 17 shows a two-electron oxidation wave at E°ox
ϭ
band is observed for all bis(allenylidenes) with respect to 0.120 V vs. Fc. In comparison to the monometallic com-
monoallenylidenes, except for compounds with nonconju- plexes allenylidene A1 and the acetylide trans-
gated linkers (Table 1). The λmax. value is almost the same [Cl(dppe)2RuϪCϵCϪCHPh2] (B),[40] we observed that for
for 4d and 5d, λmax. ϭ 520 and 522 nm respectively, with the the bi- or trimetallic species the reduction and the oxi-
m-phenyl linker. By contrast, the decrease in the absorption dation(s) were more difficult to perform. This difficulty re-
sults from electronic communication through the bridge be-
tween one metal center and the other, and notably from the
donor effect of the neutral acetylideϪruthenium group(s)
Figure 5. Cyclic voltammetry of 17; Bu4NPF6 (0.1 m) in CH2Cl2;
Figure 4. UV/Vis spectra of 4c (---), and 5c (—) in CH2Cl2
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v ϭ 100 mV·sϪ1
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453

S. Rigaut, J. Perruchon, S. Guesmi, C. Fave, D. Touchard, P. H. Dixneuf
FULL PAPER
Table 2. Electrochemistry and optical data for complexes 12 and 17
CV[a]
∆E [mV]
UV/Vis[b]
λmax (MLCT) [nm]
E°ox [V]
E°red [V]
∆E [mV]
ε [molϪ1·L·cmϪ1
]
12
17
A1
B
ϩ0.140
ϩ0.120
60
60
Ϫ1.170
Ϫ1.240
Ϫ1.030
60
60
60
764
782
504
360
763
63000
84000
18000
6000
ϩ0.020
ϩ0.310
60
60
C
Ϫ1.380
60
109000
[a]
Sample 1 mm; Bu4NPF6[b(]0.1 m) in CH2Cl2; v ϭ 100 mV sϪ1; potentials are reported in V vs. ferrocene as an internal standard.
Reversible redox processes. In CH2Cl2.
and from the withdrawing power of the cationic tuning of their properties. In addition, the original step-
allenylideneϪruthenium moiety. In analogy to allenylidene by-step synthesis of mixed allenylideneϪacetylide di- and
and acetylide complexes, the reduction processes are attri- trimetallic complexes with nine conjugated atoms were de-
buted to the reduction of the carbon-rich bridges, and the scribed and the existence of electronic communication be-
oxidations are believed to be mainly metal-centered.[33] tween allenylidene and acetylide moieties was demon-
Interestingly, in complex 17, the two acetylide moieties are strated. As the formation of a nanoscale network is needed
oxidized at the same potential (two-electron wave). This for molecular electronic devices, these new long molecules,
shows the lack of interaction between these two metal cen- obtained via controlled preparations, are interesting
ters in an oxidation process (Figure 5), whereas the varia- alternatives to the classical bis(acetylides). Their abilities for
tion of the oxidation potential between 17 and 12 is consist- trans chlorine atom substitution with an acetylide or a cu-
ent with the presence of an additional electron donor ace- mulenic chain make them interesting building blocks for the
tylide in 17. The UV/Vis spectra of 12 and 17 present very construction of metal-containing unsaturated oligomers
high λmax. values with a large ε for the presumed MLCT at and polymers to mediate electron transfer processes.
lower energy than for A1.[6a] This phenomenon might be
attributed to the admixing of some charge-transfer charac-
ter of the acetylide to the allenylidene moiety and to the
longer conjugated bridge. Finally, the original complex 12
Experimental Section
can be considered as a bis(ruthenium) species with a delo-
calized bridge allowing nine carbon atoms to connect the
General Remarks: All reactions were performed under argon or
nitrogen with use of Schlenk techniques. The solvents were deoxy-
two ruthenium centers, and it can be compared with the
genated and dried by standard methods. Infrared spectra were re-
seven-carbon-atom bridge bis(ruthenium) complexes such
corded with a Nicolet 205FTIR spectrometer in solution for oils,
as trans-[Cl(dppe)2RuϪCϵCϪC(CH3)ϭC(H)ϪC(CH3)ϭ
CϭCϭRu(dppe)2Cl]BF4 (C).[6] The reduction potential is
slightly higher and the oxidation potential is slightly lower
for 12 than for C, both potentials are getting closer to those
of the monometallic species. Hence, as observed for bis(al-
lenylidenes), the aromatic cycle in the delocalized pathway
and the slightly longer bridge lead to a decrease in the elec-
tronic coupling between the redox centers in the mixed
complexes.
and in KBr pellets for solids. The1H (300.13 MHz), 31P
(121.50 MHz) and 13C (75.47 MHz) NMR spectra were recorded
at 25 °C with a Bruker AV300 spectrometer. Elemental analyses
were performed by the ‘‘Service Central d’Analyses du CNRS’’,
Vernaison, France and CRMPO, Rennes, France. The synthesis of
cis-[(dppe)2RuCl2] (1),[41] 2a, and 2b,[42] 1-phenyl-3-trimethyl-
silylpropynone,[43] 1,2-dibenzoylacetylene,[44] and of propargyl al-
cohols 3aϪb[25] were performed by using literature methods. Com-
pounds 3cϪd,[45] 8,[46] and 13[47], reported in this section, were pre-
viously described.
HCϵC؊(OH)C(Ph)؊p-(C6H4)؊(Ph)C(OH)؊CϵCH (3c): In a
Schlenk tube, acetylene (40 mmol) was dissolved in THF (40 mL)
at Ϫ78 °C. Then, nBuLi (18.75 mL, 30 mmol, 1.6 m in hexane) was
slowly added. The mixture was stirred at Ϫ78 °C for 30 min. In
Conclusion
This work presents the synthesis, the spectroscopic, and
the voltammetric studies of a new family of carbon-rich or- another tube, p-dibenzoylbenzene (3.57 g, 12.5 mmol) was dis-
solved in THF (10 mL) and added to the solution. The mixture
was stirred overnight at room temperature before being hydrolyzed
with a saturated NH4Cl solution (10 mL). The crude product was
extracted with diethyl ether (4 ϫ 50 mL), washed with water (3 ϫ
20 mL), and dried. Further purification was achieved by chroma-
tography over silica gel (10% diethyl ether in pentane) to afford 3c
(3.29 g) as a white powder in 78% yield. 1H NMR (CDCl3): δ ϭ
7.64Ϫ7.15 (m, 14 H, Ph), 5.68 (s, 2 H, OH), 3.31 (s, 2 H, CϵCH)
ppm. 13C{1H} NMR (CDCl3): δ ϭ 145.19Ϫ125.64 (Ph), 87.08
(CϵCH), 75.53 (CϪOH), 73.30 (CϵCH) ppm. IR: ν˜ ϭ 2146
ganometallic complexes with novel topologies. First, the
formation of stable bis(allenylidene) complexes was re-
ported, and the nature of their reduced species, which are
mainly ligand-centered, was studied by means of ESR and
IR spectroscopy. The general trends observed with polymet-
allic acetylides prevail in bis(allenylidene) species: (i) the al-
lenylidene moieties can interact substantially through a
linker if the linker is conjugated, and (ii) the UV/Vis and
the electrochemical properties significantly depend on the
nature of the linker. This opens the door to a potential fine (νCϵC) cmϪ1. HRMS (EI): m/z ϭ 338.1267; [M]ϩ; calcd. 338.1307.
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Eur. J. Inorg. Chem. 2005, 447Ϫ460

Carbon-Rich Ruthenium Complexes
HCϵC؊(OH)C(Ph)؊m-(C6H4)؊(Ph)C(OH)؊CϵCH (3d): By the ppm. 13C{1H} NMR (CDCl3): δ ϭ 140.82Ϫ125.97 (Ph), 84.87
FULL PAPER
same procedure, from commercial m-dibenzoylbenzene (3.58 g), 3d
(CϵC), 83.24 (CϵCH), 74.25 (CϵCH), 64.88 (CϪOH) ppm. IR:
(3.04 g) was obtained as a white powder in 72% yield. 1H NMR ν˜ ϭ 2121 (νCϵC) cmϪ1. HRMS (EI): m/z ϭ 286.0989; [M]ϩ; calcd.
(CDCl3): δ ϭ 7.99Ϫ7.21 (m, 14 H, Ph), 3.34 (s, 2 H, OH), 2.83 (s, 286.0994. C20H14O2 (286.33): calcd. C 83.90, H 4.93; found C
2 H, CϵCH) ppm. 13C{1H} NMR (CDCl3): δ ϭ 144.56Ϫ123.44 83.99, H 4.98.
(Ph), 86.25 (CϵCH), 75.73 (CϪOH), 74.37 (CϵCH) ppm. IR: ν˜ ϭ
1-[3,5-Bis(1-hydroxy-1-phenylprop-2-ynyl)phenyl]-1-phenylpropynol
(6): By the same procedure as that for 3h, from 1,3,5-tribenzoylben-
2113 (νCϵC) cmϪ1. HRMS (EI): m/z ϭ 338.1270; [M]ϩ, calcd.
338.1307.
zene(4.88 g, 12.5 mmol), compound 6 (4.09 g) was obtained in 70%
1
yield as a white powder. H NMR (CDCl3): δ ϭ 7.89Ϫ7.12 (m, 18
H, Ph), 5.67 (s, 3 H, OH), 3.24 (s, 3 H, CϵCH) ppm. 13C{1H}
NMR (CDCl3): δ ϭ 145.94Ϫ122.91 (Ph), 87.11 (CϵCH), 75.35
(CϪOH), 73.55 (CϵCH) ppm. IR: ν˜ ϭ 2113 (νCϵC) cmϪ1. HRMS
(EI): m/z ϭ 468.1744 [M]ϩ; calcd. 468.1725. C33H24O3 (468.55):
calcd. C 84.60, H 5.16; found C 84.75, H 5.28.
HCϵC؊(OH)C(Ph)؊2,5-(thiophene)؊(Ph)C(OH)؊CϵCH (3e):
nBuLi (6.74 mL, 10.7 mmol, 1.6 m) was added dropwise to a solu-
tion of thiophene (378 mg) in THF (20 mL) at Ϫ78 °C. After stir-
ring for 1 h, 1-phenyl-3-trimethylsilylpropynone (2 g, 9.88 mmol)
dissolved in THF (10 mL) was also added dropwise. The resulting
mixture was stirred for 15 min at Ϫ78 °C and for 12 h at room
temperature. Then, water (15 mL) and tetrabutylammoniumfluor-
ide solution (18 mL, 1 m in THF) were added slowly, and the re-
sulting mixture was stirred at room temperature for 2 h . The solu-
tion was extracted with diethyl ether (3 ϫ 50 mL), and the organic
layer was washed with aqueous solution of NH4Cl. After drying
with MgSO4, the solvents were evaporated to afford a brownish oil.
Further purification was achieved by flash chromatography on sil-
ica gel with a mixture of diethyl ether/pentane as eluent to give 3e
(1.62 g) as a white solid in 52% yield. 1H NMR (CDCl3): δ ϭ
7.71Ϫ7.28 (m, 10 H, Ph), 6.88 and 6.82 (2 H, thiophene), 2.92 (s,
2 H, OH), 2.84 (s, 2 H, CϵCH) ppm. 13C{1H} NMR (CDCl3): δ ϭ
4-Ethynylbenzophenone (8): In a Schlenk tube, p-bromobenzo-
phenone (2.6 g, 9.9 mmol), CuI (180 mg, 0.99 mmol), and
[PdCl2(PPh3)2] (690 mg, 0.495 mmol) were dissolved in Et3N
(40 mL) and THF (20 mL). Then, trimethylacetylene (1.81 mL,
1.386 mmol) was added, and the mixture was stirred for 48 h at
50 °C. After cooling, the solvent was removed and the crude prod-
uct was extracted with diethyl ether and filtered through a celite
pad. After evaporation, a yellow solid was obtained. In a flask,
2.4 g of this compound was dissolved in a mixture of THF/MeOH
(25 mL) and KOH (12 mL, 1.6 m) was added slowly. The resulting
dark mixture was stirred for 1 h at room temperature, and then the
solvents were evaporated off. Purification, first by flash chromatog-
raphy (silica gel, diethyl ether) and then by recrystallization in pen-
tane, afforded 8 (1.51 g) as a pale yellow solid in 85% yield. 1H
NMR (CDCl3): δ ϭ 7.85Ϫ7.38 (m, 9 H, Ph), 3.22 (s, 1 H, CϵCH)
ppm. 13C{1H} NMR (CDCl3): δ ϭ 195.93 (CO) 137.46Ϫ126.30
(Ph), 82.87 (CϵCH), 80.21 (CϵCH) ppm. IR: ν˜ ϭ 2150 (νCϵC),
1647 (νCO) cmϪ1. HRMS (EI): m/z ϭ 206.0730 [M]ϩ; calcd.
206.0732. C15H10O (206.24): calcd. C 87.36, H 4.89; found C 87.15,
H 4.87.
150.07Ϫ149.83
(Cquat
,
thiophene),
143.3Ϫ125.8
(Ph),
124.96Ϫ124.91(CH, thiophene), 85.56 and 85.51 (CϵCH), 75.17
and 75.14 (CϪOH), 71.78 (CϵCH) ppm. IR: ν˜
ϭ 2152
(νCϵC) cmϪ1. HRMS (EI): m/z ϭ 344.0855 [M]ϩ; calcd. 344.0871.
C22H16O2S (344.43): calcd. C 76.72, H 4.68; found C 76.42, H 4.58.
HC ϵC؊(OH)C(Ph)؊5 , 5Ј- (2 , 2Ј- bi th io ph en e)؊( Ph )C
(OH)؊CϵCH (3f): By the same procedure, from 2,2Ј-bithiophene
(1 g, 6.0 mmol), nBuLi (8.25 mL, 13.2 mmol), and 1-phenyl-3-tri-
methylsilylpropynone (2.67 g, 13.2 mmol), compound 3f (1.5 g) was
obtained in 74% yield as a brownish oil. 1H NMR (CDCl3): δ ϭ
4,4Ј-Bis(ethynyl)benzophenone (13): Starting from 4,4Ј-dibromo-
benzophenone (1.69 g) and using the same procedure as that for
the formation of 8, we obtained 13 (0.98 g) as a pale yellow solid
in 95% yield. 1H NMR (CDCl3): δ ϭ 7.72Ϫ7.57 (m, 8 H, Ph), 3.23
(s, 2 H, CϵCH) ppm. 13C{1H} NMR (CDCl3): δ ϭ 195.06 (CO),
137.10Ϫ126.56 (Ph), 82.76 (CϵCH), 80.35 (CϵCH) ppm. IR: ν˜ ϭ
2158 (νCϵC), 1645 (νCO) cmϪ1. HRMS (EI): m/z ϭ 230.0730 [M]ϩ;
calcd. 230.0732. C17H10O (230.27): calcd. C 88.67, H 4.38; found
C 88.86, H 4.48.
3
7.71Ϫ7.21 (m, 10 H, Ph), 6.94 (d, JH,H ϭ 4 Hz, 2 H, thiophene),
3
6.87 (d, JH,H ϭ 4 Hz, 2 H, thiophene), 3.31 (s, 2 H, OH), 2.86 (s,
2 H, CϵCH) ppm. 13C{1H} NMR (CDCl3): δ ϭ 148.63 and 143.39
(s, Cquat, thiophene) 137.91Ϫ125.77 (Ph), 126.01 and 123.04 (CH,
thiophene), 85.45 (CϵCH), 75.28 (CϪOH), 71.70 (CϵCH) ppm.
IR: ν˜ ϭ 2149 (νCϵC) cmϪ1. HR-MS (EI): m/z ϭ 426.0730 [M]ϩ;
calcd. 426.0748. C26H18O2S2 (426.56): calcd. C 73.21, H 4.25;
found C 73.10, H 4.21.
HCϵC؊(OH)C(Ph)؊5,5ЈЈ-(2,2Ј:5Ј,2ЈЈ-terthiophene)؊(Ph)C-
(OH)؊CϵCH (3g): By the same procedure, from 2,2Ј,5Ј,2ЈЈ-ter-
thiophene (248 mg, 1.0 mmol), nBuLi (1.37 mL, 2.2 mmol) and 1-
phenyl-3-(trimethylsilyl)propynone (445 mg, 2.2 mmol), compound
3g (300 mg) was obtained in 59% yield as a brownish oil. 1H NMR
(CDCl3): δ ϭ 7.71Ϫ7.23 (m, 10 H, Ph), 6.98 (m, 4 H, thiophene),
Synthesis of Monoallenylidene Ruthenium Complexes (4aϪb, X ϭ
PF6; 4cϪh, X ϭ OTf): Dichloromethane (50 mL) was added to a
mixture of [Cl(dppe)2Ru][X] (2) (0.5 mmol) and dipropargylic al-
cohol (3) (1 mmol). The resulting mixture was stirred at room tem-
perature for 24 h, and the solvent was pumped to dryness. The
resulting solid was washed with diethyl ether (4 ϫ 25 mL) in order
to eliminate the excess of organic reactant. Further purification was
achieved by biphasic recrystallization in dichloromethane/pentane
(1:2) to afford monoallenylidene complexes (4aϪh) as powdery
solids.
3
6.91 (d, 2 H, JH,H ϭ 4 Hz, thiophene), 3.31 (s, 2 H, OH), 2.86 (s,
2 H, CϵCH) ppm. 13C{1H} NMR (CDCl3): δ ϭ 148.85 and 143.66
(s, Cquat, thiophene) 136.54Ϫ126.11 (Ph), 124.87, 123.38 and 110.10
(CH, thiophene), 85.74 (CϵCH), 75.72 (CϪOH), 72.16 (CϵCH)
ppm. IR: ν˜ ϭ 2146 (νCϵC) cmϪ1. HRMS (EI): m/z ϭ 508.0633
[M]ϩ; calcd. 508.0625. C30H20O2S3 (508.68): calcd. C 70.84, H 3.96;
found C 70.52, H 3.78.
trans-[Cl(dppe)2Ru؍C؍C؍C(H)؊p-(C6H4)؊C(H)(OH)-
(CϵC؊H)][PF6] (4a): From 3a (186 mg), complex 4a (486 mg) was
obtained as a deep red crystalline solid in 71% yield. 1H NMR
5
HCϵC؊(OH)C(Ph)؊CϵC؊(Ph)C(OH)؊CϵCH (3h): By the (CD2Cl2): δ ϭ 9.20 (quint, JPH ϭ 2.6 Hz, 1 H, RuϭCϭCϭCH),
4
same method as that for the formation of 3c or 3d, from 1,2-diben-
zoylacetylene (2.93 g, 1.25 mmol), compound 3h (2.90 g) was ob-
tained as a white solid in 81% yield. 1H NMR (CDCl3): δ ϭ
7.80Ϫ7.33 (m, 10 H, Ph), 3.61 (s, 2 H, OH), 2.76 (s, 2 H, CϵCH)
7.53Ϫ6.88 (m, 44 H, Ph) 5.44 [d broad, JH,H ϭ 2 Hz, 1 H,
HC(OH)], 3.01 (m, 4 H, CH2 dppe), 2.81 (m, 4 H, CH2 dppe), 2.72
4
(d, JH,H ϭ 2 Hz, 1 H, CϵCH) ppm. 13C{1H} NMR (CD2Cl2):
2
3
δ ϭ 320.76 (quint, JP,C ϭ 14.4 Hz, RuϭC), 221.91 (quint, JP,C
ϭ
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455

S. Rigaut, J. Perruchon, S. Guesmi, C. Fave, D. Touchard, P. H. Dixneuf
2.2 Hz, RuϭCϭC), 151.66 (RuϭCϭCϭC), 146.57Ϫ128.39 (Ph), 15 Hz, RuϭC), 202.24 (RuϭCϭC), 164.12 (RuϭCϭCϭC),
FULL PAPER
1
83.42 (CϵCH), 74.87 (CϵCH), 63.95 (CϪOH), 29.42 (quint, JP,C
ϩ 3JP,C ϭ 23 Hz, PCH2CH2P) ppm. 31P NMR (CD2Cl2): δ ϭ 40.0 74.09 (CϵCH), 27.46 (quint, JP,C ϩ JP,C ϭ 23 Hz, PCH2CH2P)
(s, dppe), Ϫ143.9 (sept., 1JPF ϭ 713 Hz, PF6) ppm. IR: ν˜ ϭ 1939 (s, ppm. 31P NMR (CD2Cl2): δ ϭ 41.0 (s, dppe) ppm. IR: ν˜ ϭ 1928
νCϭCϭC), 841 (s, νPF) cmϪ1. C64H56ClF6OP5Ru·CH2Cl2 (1246.53): (s, νCϭCϭC) cmϪ1. HRMS (FAB): m/z ϭ 1341.2076 [M]ϩ; calcd.
150.86Ϫ125.84 (Ph, thiophene), 85.17 (CϵCH), 76.43 (CϪOH),
1
3
calcd. C 58.64, H 4.39; found C 58.76, H 4.61.
1341.2081. C79H64ClF3O4P4RuS3 (1458.92): calcd. C 63.67, H 4.33;
found C 63.25, H 4.19.
trans-[Cl(dppe)2Ru؍C؍C؍C(H)؊2,5-(thiophene)؊C(H)(OH)-
(CϵC؊H)][PF6] (4b): From compound 3b (192 mg), complex 4b trans-[Cl(dppe)2Ru؍C؍C؍C(Ph)؊5,5ЈЈ-(2,2Ј:5Ј2ЈЈ-terthiophene)؊
(257 mg) was obtained as a red crystalline solid in 41% yield. 1H
C(Ph)(OH)(CϵC؊H)][CF3SO3] (4g). From compound 3g
5
NMR (CD2Cl2): δ ϭ 8.78 (quint, JPH ϭ 2.6 Hz, 1 H, RuϭCϭCϭ
(508 mg), complex 4g (452 mg) was obtained as a deep blue crystal-
CH), 7.32Ϫ6.85 (m, 42 H, Ph, C4H2S) 5.39 (d broad, 4JH,H ϭ 2 Hz, line solid in 58% yield. H NMR (CD2Cl2): δ ϭ 7.78Ϫ6.78 (m, 56
1
4
C(OH)H), 2.68 (d, JH,H ϭ 2 Hz, ϵCH), 2.99 (m, 4 H, dppe),
H, Ph ϩ terthiophene) 4.95 (s broad, 1 H, OH), 3.05 (s, 1 H, ϵCH),
2.85(m, 4 H, dppe) ppm. 31P NMR (CD2Cl2): δ ϭ 41.8 (s, dppe), 2.98 (m, 4 H, dppe), 2.79 (m, 4 H, dppe) ppm. 13C{1H} NMR
Ϫ143.5 (sept., 1JPF ϭ 713 Hz, PF6) ppm. IR: ν˜ ϭ 1927 (s, νCϭCϭC),
841 (s, νPF) cmϪ1. C62H54ClF6OP5RuS (1252.56): calcd. C 59.45, H
4.35; found C 59.60, H 4.35.
(CD2Cl2): δ ϭ 294.48 (quint, JP,C ϭ 15 Hz, RuϭC), 206.55 (Ruϭ
CϭC), 169.52 (RuϭCϭCϭC), 151.44Ϫ126.23 (Ph, thiophene)
2
1
85.81 (CϵCH), 76.95 (CϪOH), 74.25 (CϵCH), 27.41 (quint, JP,C
ϩ 3JP,C ϭ 23 Hz, PCH2CH2P) ppm. 31P NMR (CD2Cl2): δ ϭ 41.2
(s, dppe) ppm. IR: ν˜ ϭ 1922 (s, νCϭCϭC) cmϪ1. HRMS (FAB):
m/z ϭ 1423.1970 [M]ϩ; calcd. 1423.1958).
trans-[Cl(dppe)2Ru؍C؍C؍C(Ph)؊p-(C6H4)؊C(Ph)(OH)-
(CϵC؊H)][CF3SO3] (4c): From compound 3c (338 mg), complex
4c (568 mg) was obtained as a deep red crystalline solid in 81%
yield. 1H NMR (CD2Cl2): δ ϭ 7.75Ϫ6.68 (m, 54 H, Ph) 4.90 (s trans-[Cl(dppe)2Ru؍C؍C؍C(Ph)؊(CϵC)؊C(Ph)(OH)-
broad, 1 H, OH), 3.08 (m, 4 H, dppe), 3.04 (s, ϵCH), 2.92 (m, 4 (CϵC؊H)][CF3SO3] (4h): From compound 3h (286 mg), complex
H, dppe) ppm. 13C{1H} NMR (CD2Cl2): δ ϭ 307.06 (quint, 2JP,C ϭ
4h (506 mg) was obtained as a deep red solid in 75% yield. 1H
14.5 Hz, RuϭC), 215.14 (RuϭCϭC), 160.25 (RuϭCϭCϭC), NMR (CD2Cl2): δ ϭ 7.85Ϫ6.66 (m, 50 H, Ph), 3.08 (m, 8 H, dppe),
1
148.97Ϫ125.99 (Ph), 121.43 (q, JC,F ϭ 319 Hz, CF3SO3), 85.17
3.06 (s, ϵCH) ppm. 13C{1H} NMR (CD2Cl2): δ ϭ 301.20 (quint,
2JP,C ϭ 15 Hz, RuϭC), 229.68 (RuϭCϭC), 142.24 and 141.05 (s,
1
(CϵCH), 76.43 (CϪOH), 74.09 (CϵCH), 27.46 (quint, JP,C
ϩ
3JP,C ϭ 23 Hz, PCH2CH2P) ppm. 31P NMR (CD2Cl2): δ ϭ 38.2 (s, Ph), 134.77 (RuϭCϭCϭC), 133.92Ϫ125.95 (Ph), 120.89 (q,
dppe) ppm. IR: ν˜ ϭ 1921 (s, νCϭCϭC) cmϪ1. HRMS (FAB): m/z ϭ
1JC,F ϭ 320 Hz, CF3SO3), 95.60 and 91.04 (CϵC), 82.17 (CϵCH),
1253.2660 [M]ϩ; calcd. 1253.2640. C77H64ClF3O4P4RuS (1402.85): 75.07 (CϵCH), 65.59 (CϪOH), 27.25 (quint, JP,C
ϩ ϭ
3JP,C
1
calcd. C 65.93, H 4.60; found C 65.51, H 4.64.
23 Hz, PCH2CH2P) ppm. 31P NMR (CD2Cl2): δ ϭ 38.0 (s, dppe)
ppm. IR: ν˜ ϭ 1921 (s, νCϭCϭC) cmϪ1. HRMS (FAB): m/z ϭ
1201.2336 [M]ϩ; calcd. 1201.2327. C73H60ClF3O4P4RuS (1350.76):
calcd. C 64.91, H 4.48; found C 64.97, H 4.47.
trans-[Cl(dppe)2Ru؍C؍C؍C(Ph)؊m-(C6H4)؊C(Ph)(OH)-
(CϵC؊H)][CF3SO3] (4d): From compound 3d (338 mg), complex
4d (519 mg) was obtained as a deep red crystalline solid in 74%
yield. 1H NMR (CD2Cl2): δ ϭ 7.78Ϫ6.58 (m, 54 H, Ph) 4.99 (s Synthesis of Bis(allenylidene)ruthenium Complexes (5a؊b, X؍PF6;
broad, 1 H, OH), 3.09 (m, 4 H, dppe), 3.05 (s, ϵCH), 2.94 (m, 4 5c؊h, X؍OTf): To a mixture of [Cl(dppe)2Ru][X] (0.5 mmol) and
H, dppe) ppm. 13C{1H} NMR (CD2Cl2): δ ϭ 308.12 (quint, 2JP,C ϭ
dipropargylic alcohol (3) (0.2 mmol), dichloromethane (50 mL) was
14.5 Hz, RuϭC), 216.17 (RuϭCϭC), 161.25 (RuϭCϭCϭC), added. The resulting mixture was stirred at room temperature for
1
148.98Ϫ126.90(Ph), 121.38 (q, JC,F ϭ 320 Hz, CF3SO3), 85.18
7 d, and the solvent was evaporated. The resulting solid was washed
with diethyl ether (4 ϫ 25 mL) in order to eliminate the organic
1
(CϵCH), 76.48 (CϪOH), 74.01 (CϵCH), 27.40 (quint, JP,C
ϩ
3JP,C ϭ 23 Hz, PCH2CH2P) ppm. 31P NMR (CD2Cl2): δ ϭ 38.2 (s, reactant excess, and was precipitated three times with 60 mL of
dppe) ppm. IR: ν˜ ϭ 1921 (s, νCϭCϭC) cmϪ1. HRMS (FAB): m/z ϭ
pentane after dissolution in dichloromethane (20 mL). Further
1253.2670 [M]ϩ; calcd. 1253.2640. C77H64ClF3O4P4RuS (1402.85): purification was achieved by biphasic recrystallization in dichloro-
calcd. C 65.93, H 4.60; found C 65.61, H 4.69.
methane/pentane (1:2) to afford the bis(allenylidene) complexes
5aϪh as powdery solids.
trans-[Cl(dppe)2Ru؍C؍C؍C(Ph)؊2,5-(thiophene)؊C(Ph)(OH)-
(CϵC؊H)][CF3SO3] (4e): From compound 3e (344 mg), complex trans-[Cl(dppe)2Ru؍C؍C؍C(H)؊p-(C6H4)؊(H)C؍C؍C؍RuCl-
4e (452 mg) was obtained as a deep violet crystalline solid in 64%
(dppe)2][PF6]2 (5a): From 3a (36 mg), complex 5a (208 mg) was ob-
3
1
yield. 1H NMR (CD2Cl2): δ ϭ 7.68 (quint, JPH ϭ 4 Hz, 1 H,
tained as a blue crystalline solid in 45% yield. H NMR (CD2Cl2):
5
thiophene), 7.60Ϫ6.78 (m, 51 H, PhϩC4H2S) 4.85 (s broad, 1 H, δ ϭ 9.64 (quint, JPH ϭ 2.8 Hz, 2 H, RuϭCϭCϭCH), 7.31Ϫ6.46
OH), 2.95 (s, ϵCH), 2.94 (m, 4 H, dppe), 2.76(m, 4 H, dppe) ppm. (m, 84 H, Ph), 2.99 (m, 16 H, dppe) ppm. 13C{1H} NMR (CD2Cl2):
2
2
13C{1H} NMR (CD2Cl2): δ ϭ 288.47 (quint, JP,C ϭ 15 Hz, Ruϭ δ ϭ 326.28 (quint, JP,C ϭ 15 Hz, RuϭC), 241.33 (RuϭCϭC),
1
C), 202.24 (RuϭCϭC), 164.12 (RuϭCϭCϭC), 150.86Ϫ125.84 152.01 (RuϭCϭCϭC), 143.24Ϫ128.41 (Ph), 29.52 (quint, Jpc
ϩ
(Ph, thiophene) 85.17 (CϵCH), 76.43 (CϪOH), 74.09 (CϵCH), 3Jpc ϭ 23 Hz, PCH2CH2P) ppm. 31P NMR (CD2Cl2): δ ϭ 39.2 (s,
1
3
27.46 (quint, JP,C ϩ JP,C ϭ 23 Hz, PCH2CH2P) ppm. 31P NMR
dppe) ppm. IR: ν˜ ϭ 1918 (s, νCϭCϭC) cmϪ1. C116H102Cl2F12P10Ru2
(2306.85): calcd. C 60.44, H 4.46; found C 59.87, H 4.28.
(CD2Cl2): δ ϭ 41.0 (s, dppe) ppm. IR: ν˜ ϭ 1928 (s, νCϭCϭC) cmϪ1
.
C75H62ClF3O4P4RuS2 (1408.61): calcd. C 63.94, H 4.44; found C
63.77, H 4.39.
trans-[Cl(dppe)2Ru؍C؍C؍C(H)؊2,5-(thiophene)؊(H)C؍C؍C؍
RuCl(dppe)2][PF6]2 (5b): From 3b (39 mg), complex 5b (224 mg)
trans-[Cl(dppe)2Ru؍C؍C؍C(Ph)؊5,5Ј-(2,2Ј-bithiophene)؊C(Ph)- was obtained as a deep blue solid in 49% yield. 1H NMR (CD2Cl2):
(OH)(CϵC؊H)][CF3SO3] (4f): From compound 3f (426 mg), com-
plex 4f (477 mg) was obtained as a dark violet solid in 64% yield.
δ ϭ 9.36 (m, 2 H, RuϭCϭCϭCH), 7.31Ϫ6.90 (m, 82 H, Ph, thio-
phene), 3.06 (m, 16 H, dppe) ppm. 13C{1H} NMR (CD2Cl2): δ ϭ
2
1H NMR (CD2Cl2): δ ϭ 7.69Ϫ6.78 (m, 54 H, Ph, bithiophene) 4.92 310.53 (quint, JP,C ϭ 17 Hz, RuϭC), 237.55 (RuϭCϭC), 158.33
(s broad, 1 H, OH, 3.01 (s, ϵCH), 2.95 (m, 4 H, dppe), 2.79 (m, 4
(RuϭCϭCϭC), 134.31Ϫ128.37 (Ph, thiophene), 29.76 (quint, 1JP,C
ϩ 3JP,C ϭ 23 Hz, PCH2CH2P) ppm. 31P NMR (CD2Cl2): δ ϭ 39.1
H, dppe) ppm. 13C{1H} NMR (CD2Cl2): δ ϭ 288.47 (quint, 2JP,C ϭ
456
© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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Eur. J. Inorg. Chem. 2005, 447Ϫ460

Carbon-Rich Ruthenium Complexes
(s, dppe) ppm. IR: ν˜
C114H100Cl2F12P10Ru2S (2312.22): calcd. C 59.20, H 4.36; found C
59.40, H 4.76.
FULL PAPER
2254.3336. C136H112Cl2F6P8O6Ru2S5 (2637.54): calcd. C 61.93, H
4.28; found C 62.07, H 4.19.
ϭ
1913 (s, νCϭCϭC) cmϪ1
.
trans-[Cl(dppe)2Ru؍C؍C؍C(Ph)؊(CϵC)؊(Ph)C؍C؍C؍RuCl-
(dppe)2][CF3SO3]2 (5h): From 3h (57 mg), complex 5h (203 mg) was
obtained as a deep blue solid in 42% yield. 1H NMR (CD2Cl2):
δ ϭ 7.74Ϫ6.67 (m, 90 H, Ph), 2.98 (m, 16 H, dppe) ppm. 31P NMR
trans-[Cl(dppe)2Ru؍C؍C؍C(Ph)؊p-(C6H4)؊(Ph)C؍C؍C؍
RuCl(dppe)2][CF3SO3]2 (5c): From 3c (68 mg), complex 5c (385 mg)
was obtained as a deep blue solid in 78% yield. 1H NMR (CD2Cl2):
(CD2Cl2): δ ϭ 37.8 (s, dppe) ppm. IR: ν˜ ϭ 1921 (s, νCϭCϭC) cmϪ1
HRMS (FAB): m/z ϭ 2116.3666 [M]ϩϩ; calcd. 2116.3659.
.
δ ϭ 7.33Ϫ6.56 (m, 94 H, Ph), 3.04 (m, 8 H, dppe), 2.79 (m, 8 H,
dppe) ppm. 13C{1H} NMR (CD2Cl2): δ ϭ 310.98 (quint, JP,C
ϭ
2
15 Hz, RuϭC), 228.87 (RuϭCϭC), 158.17 (RuϭCϭCϭC),
trans-[3,5-Bis[Cl(dppe)2Ru؍C؍C؍C(Ph)]2؊(C6H3)؊C(Ph)-
(OH)(CϵC؊H)][CF3SO3]2 (7): From (36 mg), complex
1
145.91Ϫ128.41 (s, Ph), 121.51 (q, JC,F ϭ 320 Hz, CF3SO3), 27.88
6
7
1
(quint, JP,C
ϩ
3JP,C ϭ 23 Hz, PCH2CH2P) ppm. 31P NMR
1
(208 mg) was obtained as a deep red solid in 63% yield. H NMR
(CD2Cl2): δ ϭ 7.75Ϫ6.48 (m, 98 H, Ph), 4.91(s broad, 1 H, OH),
3.07 (m, 8 H, dppe), 3.05 (s,1 H, CϵCH), 2.93 (m, 8 H, dppe) ppm.
(CD2Cl2): δ ϭ 38.0 (s, dppe) ppm. IR: ν˜ ϭ 1912 (s, νCϭCϭC) cmϪ1
HRMS (FAB): m/z calcd. 2317.3493.
.
ϭ
2317.3563 [M]ϩϩ
;
C130H110Cl2F6P8O6Ru2S2 (2467.26): calcd. C 63.29, H 4.49; found
C 62.49, H 4.45.
2
13C{1H} NMR (CD2Cl2): δ ϭ 311.55 (quint, JP,C ϭ 15 Hz, Ruϭ
C), 225.52 (RuϭCϭC), 156.73 (RuϭCϭCϭC), 149.38Ϫ127.47
1
trans-[Cl(dppe)2Ru؍C؍C؍C(Ph)؊m-(C6H4)؊(Ph)C؍C؍C؍
RuCl(dppe)2][CF3SO3]2 (5d): From 3d (64 mg), complex 5d
(Ph), 121.55 (q, JC,F
ϭ 320 Hz, CF3SO3), 86.30(CϵCH),
1
77.62(CϪOH), 73.09(s, CϵCH), 28.11 (quint, JP,C
ϩ ϭ
3JP,C
1
23 Hz, PCH2CH2P) ppm. 31P NMR (CD2Cl2): δ ϭ 38.1 (s,
dppe) ppm. IR: ν˜ ϭ 1921 (s, νCϭCϭC) cmϪ1. HRMS (FAB):
(222 mg) was obtained as a deep red solid in 45% yield. H NMR
(CD2Cl2): δ ϭ 7.72Ϫ6.78 (m, 94 H, Ph), 3.07 (m, 8 H, dppe), 2.97
(m, 8 H, dppe) ppm. 13C{1H} NMR (CD2Cl2): δ ϭ 310.01 (quint,
2JP,C ϭ 15 Hz, RuϭC), 224.21 (RuϭCϭC), 157.47 (s, RuϭCϭCϭ
m/z
ϭ
2448.3392 ([M]ϩϩ,CF3SO3Ϫ)ϩ; calcd. 2448.3960.
C139H116Cl2F6P8O7Ru2S2 (2581.41): calcd. C 64.28, H 4.50; found
C 65.51, H 4.64.
C), 145.84Ϫ128.37 (Ph), 121.55 (q, 1JC,F ϭ 320 Hz, CF3SO3), 28.15
1
(quint, JP,C
ϩ
3JP,C ϭ 23 Hz, PCH2CH2P) ppm. 31P NMR
(CD2Cl2): δ ϭ 38.8 (s, dppe) ppm. IR: ν˜ ϭ 1913 (s, νCϭCϭC) cmϪ1
HRMS (FAB): m/z calcd. 2317.3493.
2317.3507 [M]ϩϩ
130H110Cl2F6P8O6Ru2S2 (2467.26): calcd. C 63.29, H 4.49; found
.
Synthesis of (Acetylide؊allenylidene)ruthenium Complexes
ϭ
;
trans-[Cl(dppe)2Ru؍C؍CH؊p-(C6H4)؊CO؊Ph][CF3SO3] (9): In
a Schlenk tube, 2b (1.67 g, 1.55 mmol) and 4-ethynylbenzophenone
(8) (350 mg, 1.7 mmol) were dissolved in dry dichloromethane
(40 mL) and stirred at room temperature for 18 h. Then, the brown
solution was filtered, and the solvent was evaporated. The crude
product was washed with diethyl ether. Purification was achieved
by biphasic recrystallization (CH2Cl2/pentane) to afford complex 9
C
C 63.11, H 4.51.
trans-[Cl(dppe)2Ru؍C؍C؍C(Ph)؊2,5-(thiophene)؊(Ph)C؍C؍
C؍RuCl(dppe)2][CF3SO3]2 (5e): From 3e (69 mg), complex 5e
(306 mg) was obtained as a deep blue solid in 62% yield. 1H NMR
(CD2Cl2): δ ϭ 7.85Ϫ6.82 (m, 90 H, Ph), 6.30(s, 2 H, thiophene),
3.18 (m, 8 H, dppe), 2.85 (m, 8 H, dppe) ppm. 13C{1H} NMR
1
(1.42 g) as orange crystals in 71% yield. H NMR (CD2Cl2): δ ϭ
4
2
7.82Ϫ6.95 (m, 49 H, Ph), 4.82 (quint, JPH ϭ 3 Hz, 1 H, RuϭCϭ
(CD2Cl2): δ ϭ 311.53 (quint, JP,C ϭ 15 Hz, RuϭC), 237.85 (Ruϭ
CH), 2.92 (m, 8 H, dppe) ppm. 13C{1H} NMR (CD2Cl2): δ ϭ
352.01 (quint, 2JP,C ϭ 14 Hz, RuϭC), 195.41 (CO), 138.01Ϫ126.85
CϭC), 159.33 (RuϭCϭCϭC), 134.39Ϫ128.87 (Ph, thiophene),
1
1
3
121.55 (q, JC,F ϭ 320 Hz CF3SO3), 29.66 (quint, JP,C ϩ JP,C
ϭ
1
2
23 Hz, PCH2CH2P) ppm. 31P NMR (CD2Cl2): δ ϭ 39.3 (s,
dppe) ppm. IR: ν˜ ϭ 1904 (s, νCϭCϭC) cmϪ1. HRMS (FAB):
(Ph), 123.05 (q, JC,F ϭ 320 Hz, CF3SO3), 109.64 (quint, JP,C
ϭ
1
3 Hz, RuϭCϭCH), 29.16 (quint, JP,C
ϩ ϭ 23 Hz,
3JP,C
PCH2CH2P) ppm. 31P NMR (CD2Cl2): δ ϭ 36.3 (s, dppe) ppm.
IR: ν˜ ϭ 1588 (s, νCϭC), 1647 (s, νCO) cmϪ1. HRMS (FAB): m/z ϭ
1139.2186 [M]ϩ; calcd. 1139.2170. C68H58ClF3P4O4RuS (1288.69):
calcd. C 63.38, H 4.54; found C 63.40, H 4.53.
m/z
ϭ
2173.3587 [Mϩϩ
Ϫ
Hϩ]; calcd. 2173.3459.
C128H108Cl2F6P8O6Ru2S3 (2473.29): calcd. C 62.16, H 4.40; found
C 61.97, H 4.37.
trans-[Cl(dppe)2Ru؍C؍C؍C(Ph)؊5,5Ј-(2,2Ј-bithiophene)(Ph)C؍
C؍C؍RuCl(dppe)2][CF3SO3]2 (5f): From 3f (85 mg), complex 5f
(260 mg) was obtained as a deep blue solid in 51% yield. 1H NMR
trans-[Cl(dppe)2Ru؊CϵC؊p-(C6H4)؊CO؊Ph] (10): In a Schlenk
tube, complex 9 (625 mg, 0.485 mmol) was dissolved in dry di-
chloromethane (20 mL) and DBU (0.150 mL, 0.970 mmol) was ad-
ded. The solution was stirred at room temperature for 2 h and fil-
tered through neutral alumina. The solvent was evaporated to af-
ford 10 (518 mg) as a yellow solid in 92% yield. 1H NMR (CD2Cl2):
δ ϭ 7.83Ϫ6.64 (m, 49 H, Ph), 2.76 (m, 8 H, dppe) ppm. 13C{1H}
NMR (CD2Cl2): δ ϭ 195.9 (CO), 139.26Ϫ127.49 (Ph), 138.98
(CD2Cl2): δ ϭ 7.85Ϫ6.82 (m, 94 H, Ph, thiophene), 3.04 (m, 16 H,
2
dppe) ppm. 13C{1H} NMR (CD2Cl2): δ ϭ 312.24 (quint, JP,C
ϭ
17 Hz, RuϭC), 236.47 (RuϭCϭC), 158.99 (RuϭCϭCϭC),
1
135.30Ϫ128.47 (Ph, thiophene), 121.55 (q, JC,F
ϭ
320 Hz,
1
CF3SO3), 30.05 (quint, JP,C
ϩ
3JP,C ϭ 23 Hz, PCH2CH2P) ppm.
31P NMR (CD2Cl2): δ ϭ 39.6 (s, dppe) ppm. IR: ν˜ ϭ 1925 (s,
νCϭCϭC) cmϪ1. C132H110Cl2F6P8O6Ru2S4 (2555.41): calcd. C 62.07,
H 4.30; found C 61.87, H 4.20.
1
(2JP,C ϭ 15 Hz, RuϪCϵC), 115.62 (RuϪCϵC), 30.99 (quint, JP,C
ϩ 3JP,C ϭ 23 Hz, PCH2CH2P) ppm. 31P NMR (CD2Cl2): δ ϭ 48.9
(s, dppe) ppm. IR: ν˜ ϭ 2057 (s, νCϵC), 1584 (s, νCO) cmϪ1. HRMS
(FAB): m/z ϭ 1138.2076 [M]ϩ; calcd. 1138.2092. C67H57ClP4ORu
(1138.61): calcd. C 70.68, H 5.05; found C 70.08, H 4.92.
trans-[Cl(dppe)2Ru؍C؍C؍C(Ph)؊5,5ЈЈ-(2,2Ј:5Ј,2ЈЈterthiophene)؊
(Ph)C؍C؍C؍RuCl(dppe)2][CF3SO3]2(5g): From 3g (102 mg),
complex 5g (232 mg) were obtained as a deep blue solid in 44%
yield. 1H NMR (CD2Cl2): δ ϭ 7.85Ϫ6.82 (m, 96 H, Ph, thiophene),
trans-[Cl(dppe)2Ru؊CϵC؊p-(C6H4)؊C(OH)(Ph)CϵCH] (11): In
2.99 (m, 16 H, dppe) ppm. 13C{1H} NMR (CD2Cl2): δ ϭ 313.83 a Schlenk tube, acetylene (5 mmol) was dissolved in dry THF
2
(quint, JP,C ϭ 17 Hz, RuϭC), 237.85 (RuϭCϭC), 159.33 (Ruϭ
(20 mL) cooled to Ϫ78 °C. n-Butyllithium (1.6 mL, 1 mmol, 1.6 m
in hexane) was added slowly under argon and the mixture was
1
CϭCϭC), 136.30Ϫ127.37 (Ph, thiophene), 121.55 (q, JC,F
ϭ
320 Hz, CF3SO3), 30.96 (quint, 1JP,C ϩ 3JP,C ϭ 23 Hz, PCH2CH2P) stirred at Ϫ78 °C for 1 h. Then, 10 (445 mg 0.4 mmol) dissolved in
ppm. 31P NMR (CD2Cl2): δ ϭ 40.3 (s, dppe) ppm. IR: ν˜ ϭ 1929
(s, νCϭCϭC) cmϪ1. HRMS (FAB): m/z ϭ 2254.3332 [M]ϩϩ; calcd. at Ϫ78 °C and 1 h at room temperature. After evaporation of the
THF (5 mL) was added dropwise. The solution was stirred for 1 h
Eur. J. Inorg. Chem. 2005, 447Ϫ460
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© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
457

S. Rigaut, J. Perruchon, S. Guesmi, C. Fave, D. Touchard, P. H. Dixneuf
FULL PAPER
solvent, the crude product was dissolved in dichloromethane
(50 mL), washed with water and dried with magnesium sulfate.
Purification by flash chromatography (neutral alumina, dichloro-
methane) provided 11 (366 mg) as a pale yellow powder in 78%
dppe) ppm. IR: ν˜ ϭ 2053 (s, νCϵC), 1584 (s, νCO) cmϪ1. HRMS
(FAB): m/z
121H101Cl2P8ORu2 (2091.15): calcd. C 69.37, H 5.00; found C
69.12, H 4.87.
ϭ
2094.3440 [M]ϩϩ
;
calcd. 2094.3452.
C
1
yield. H NMR (CD2Cl2): δ ϭ 7.79Ϫ6.58 (m, 49 H, Ph), 2.86 (s, 1
trans-[Cl(dppe)2Ru؊CϵC؊p-(C6H4)؊C(OH)(CϵCH)؊p-
(C6H4)؊CϵC؊RuCl(dppe)2] (16): In a Schlenk tube, acetylene
(4 mmol) was dissolved in dry THF (20 mL) cooled to Ϫ78 °C, n-
butyllithium (0.8 mL, 0.5 mmol, 1.6 m in hexane) was added slowly,
and the mixture was stirred for 1 h at Ϫ78 °C. Then, 15 (500 mg,
0.238 mmol) was dissolved in dry THF (5 mL) and added dropwise
to the mixture. The solution was stirred for 30 min at Ϫ78 °C and
1 h at room temperature. The solvent was evaporated, the crude
product dissolved in dichloromethane (40 mL), washed with water,
H, CϵCH), 2.75 (s, 1 H, OH), 2.64 (m, 8 H, dppe) ppm. 13C{1H}
2
NMR (CD2Cl2): δ ϭ 144.77Ϫ135.46 (Ph), 134.89 (quint, JP,C
ϭ
15 Hz, RuϪCϵCϪ), 134.39Ϫ125.35 (Ph), 113.63 (RuϪCϵC),
1
3
30.99 (quint, JP,C ϩ JP,C ϭ 23 Hz, PCH2CH2P) ppm. 31P NMR
(CD2Cl2): δ ϭ 50.2 (s, dppe) ppm. IR: ν˜ ϭ 3050 (s, νϵCH), 2135 (s,
νCϵCH), 2065 (s, νCϵC) cmϪ1. HRMS (FAB): m/z ϭ 1164.2255
[M]ϩ; calcd. 1164.2249). C69H59ClP4ORu (1164.65): calcd. C 71.16,
H 5.11; found C 71.23, H 5.14.
trans-[Cl(dppe)2Ru؊CϵC؊p-(C6H4)؊(Ph)C؍C؍C؍RuCl- and dried with MgSO4. Purification by flash chromatography
(dppe)2][CF3SO3] (12): In a Schlenk tube 11 (300 mg, 0.258 mmol) (aluminum oxide, dichloromethane) afforded 16 (431 mg) as a yel-
1
and 2b (200 mg, 0.284 mmol) were dissolved in dichloromethane
low solid in 85% yield. H NMR (CD2Cl2): δ ϭ 7.66Ϫ6.92 (m, 88
(50 mL), and the resulting mixture was stirred at room temperature
H, Ph), 2.95 (s, 1 H, OH), 2.63 (m, 16 H, dppe), 2.58 (s, 1 H,
for 8 days. After evaporation of the solvent, the crude product was CϵCH) ppm. 13C{1H} NMR (CD2Cl2): δ ϭ 138.64Ϫ125.42 (Ph),
2
washed with ether (4 ϫ 25 mL) and precipitated three times with
60 mL of pentane after dissolution in dichloromethane (20 mL).
Purification was achieved by biphasic recrystallization (dichloro-
methane/pentane 1:2) to afford 12 (420 mg) as a deep purple solid
134.89 (quint, JP,C ϭ 15 Hz, RuϪCϵCϪ), 113.75 (RuϪCϵC),
1
86.28 (CϵCH), 74.91(CϵCH), 74.54 (CϪOH), 30.77 (quint, JP,C
ϩ 3JP,C ϭ 23 Hz, PCH2CH2P) ppm. 31P NMR (CD2Cl2): δ ϭ 50.1
(s, dppe) ppm. IR: ν
˜ ϭ 3052 (s, νϵCH), 2136 (s, νCϵCH), 2068 (s,
in 72% yield. 1H NMR (CD2Cl2): δ ϭ 7.84Ϫ6.18 (m, 89 H, Ph), νCϵC) cmϪ1. HRMS (FAB): m/z ϭ 2120.3666 [M]ϩϩ; calcd.
3.04 (m, 8 H, dppe), 2.77 (m, 8 H, dppe) ppm. 13C{1H} NMR 2120.3609. C123H106Cl2P8ORu2 (2221.4): calcd. C 69.65, H 5.04;
2
(CD2Cl2): δ ϭ 345.62 (quint, JP,C ϭ 15 Hz, RuϭC), 192.85 (Ruϭ
CϭC), 158.32 (RuϭCϭCϭC), 143.51Ϫ123.21 (Ph), 135.45 (quint,
2JP,C ϭ 15 Hz, RuϪCϵCϪ), 113.63 (RuϪCϵC), 30.71 (quint, 1JP,C
ϩ 3JP,C ϭ 23 Hz, PCH2CH2P), 27.82 (quint, 1JP,C ϩ 3JP,C ϭ 23 Hz,
PCH2CH2P), ppm. 31P NMR (CD2Cl2): δ ϭ 49.2 (s, dppe), 40.7 (s,
dppe) ppm. IR: ν˜ ϭ 2040 (s, νCϵC), 1926 (νCϭCϭC) cmϪ1. HRMS
found C 69.37, H 5.12.
trans-[{Cl(dppe)2Ru؊CϵC؊p-(C6H4)}2C؍C؍C؍RuCl(dppe)2]-
[CF3SO3] (17): In a Schlenk tube, 16 (250 mg, 0.118 mmol) and 2b
(139 mg, 0.129 mmol) were dissolved in dichloromethane (50 mL).
The mixture was stirred at room temperature for 14 d. The solvent
was removed under vacuum, and the crude product was washed
with diethyl ether. The product was precipitated three times with
60 mL of pentane after dissolution in dichloromethane (20 mL),
and purification was achieved by biphasic recrystallization (di-
chloromethane/pentane, 1:2) to afford 17 (420 mg) as a deep green
(FAB):
122H105F3Cl2O3P8Ru2S (2229.08): calcd. C 65.74, H 4.75; found
C 65.90, H 4.88.
m/z
ϭ
2079.3555
[M]ϩ;
calcd.
2079.3581.
C
trans-[Cl(dppe)2Ru؍C؍CH؊p-(C6H4)؊CO؊p-(C6H4)؊CH؍C؍
RuCl(dppe)2][CF3SO3]2 (14): In Schlenk tube 2b (1.62 g,
1
solid in 83% yield. H NMR (CD2Cl2): δ ϭ 7.57Ϫ6.20 (m, 128 H,
a
Ph), 2.94 (m, 8 H, dppe), 2.74 (m, 8 H, dppe), 2.54 (m, 8 H, dppe)
1.5 mmol) and 4,4Ј-bis(ethynyl)benzophenone (13) (154 mg,
0.67 mmol) were dissolved in dry dichloromethane (30 mL), and
the mixture was stirred for 18 h at room temperature. After fil-
tration and evaporation of the solvent, the crude product was
washed with ether (4 ϫ 40 mL) and recrystallized by the biphasic
method to afford 14 (1.31 g) as orange crystals in 82% yield. 1H
NMR (CD2Cl2): δ ϭ 7.67Ϫ5.77 (m, 88 H, Ph), 4.74 (quint,2H
4JPH ϭ 3 Hz, RuϭCϭCH), 3.01 (m, 16 H, dppe) ppm. 13C{1H}
2
ppm. 13C{1H} NMR (CD2Cl2): δ ϭ 342.32 (quint, JP,C ϭ 14 Hz,
RuϭC),
190.85
(RuϭCϭC),
154.32
(RuϭCϭCϭC),
2
138.64Ϫ125.42 (Ph), 134.29 (quint, JP,C ϭ 15 Hz, RuϪCϵCϪ),
116.75 (s, RuϪCϵC), 30.69 (quint, JP,C
1
ϩ
3JP,C ϭ 23 Hz,
1
PCH2CH2P), 28.77 (quint, JP,C
ϩ
3JP,C ϭ 23 Hz, PCH2CH2P)
ppm. 31P NMR (CD2Cl2): δ ϭ 49.3 (s, dppe), 40.6 (s, dppe) ppm.
IR: ν˜ ϭ 2008 (s, νCϵC), 1912 (s, νCϭCϭC) cmϪ1. HRMS (FAB):
ϭ ; calcd. 3035.4941. C176 H152Cl3F3
3035.4966 [M]ϩϩ
2
m/z
NMR (CD2Cl2): δ ϭ 354.02 (quint, JP,C ϭ 14 Hz, RuϭC), 196.81
1
O3P12Ru3S (3185.46): calcd. C 66.36, H 4.81; found C 66.65, H
4.90.
(CO), 138.48Ϫ126.95 (Ph), 123.15 (q, JC,F ϭ 320 Hz, CF3SO3),
3
1
109.84 (quint, JP,C ϭ 3 Hz, RuϭCϭCH), 30.16 (quint, JP,C
ϩ
3JP,C ϭ 23 Hz, PCH2CH2P) ppm. 31P NMR (CD2Cl2): δ ϭ 37.3 (s,
dppe) ppm. IR: ν˜ ϭ 1592 (s, νCϭC), 1633 (νCO) cmϪ1. HRMS
(FAB): m/z
ϭ
2095.3564 [M]ϩϩ
;
calcd. 2095.3530.
Acknowledgments
C123H106Cl2F6O7P8Ru2S2 (2295.15): calcd. C 61.68, H 4.46; found
C 61.55, H 4.27.
We thank the French-Ministry MNESR for the award of a thesis
grant to J. P., CNRS and the University of Rennes 1 for support,
Dr. P. Guenot (Rennes) for helpful discussion, and Prof. P. Turek
(Strasbourg) for help in structure determination.
trans-[Cl(dppe)2 Ru؊CϵC؊p-(C6 H4 )؊CO؊p-(C6 H4 )؊
CϵC؊RuCl(dppe)2] (15): In a Schlenk tube 14 (1.31 g, 0.55 mmol)
was dissolved in dry dichloromethane (30 mL) and DBU
(0.175 mL, 1.10 mmol) was added slowly. The solution was stirred
at room temperature for 2 h. After filtration through neutral alum-
ina and evaporation of the solvent, 15 (1.01 g) was obtained as a
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© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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Eur. J. Inorg. Chem. 2005, 447Ϫ460

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