Synthesis of ruthenium acetylides: New building blocks for molecular electronics

Article abstract of DOI:10.1016/S0022-328X(02)02101-0

Several ruthenium(II) mono(acetylides) trans-[Cl (dppe)₂Ru-(C≡C)_n-R] (n = 1-4; R = SiMe₃, H) and bis(acetylide) trans-[(dppe)₂Ru(-(C≡C)₂-R)₂] (R = SiMe₃, H) were selectively obtained and could be used as a new set of building blocks for rigid rodlike structures and further assemblies. Especially, the oxidative coupling of trans-[Cl (dppe)₂Ru-(C≡C)₃-H] with Cu(OAc)₂ led to the formation of the first Ruthenium(II) binuclear species with 12 carbon atoms between the remote metals. This compound shows two reversible redox processes.

Full text of DOI:10.1016/S0022-328X(02)02101-0

Journal of Organometallic Chemistry 670 (2003) 37Á44
/
www.elsevier.com/locate/jorganchem
Synthesis of ruthenium acetylides: new building blocks for molecular
electronics
Ste´phane Rigaut *, Johann Perruchon, Luc Le Pichon, Daniel Touchard *,
Pierre H. Dixneuf
Institut de Chimie de Rennes, UMR 6509 CNRS-Universite´ de Rennes: Organome´talliques et Catalyse, Campus de Beaulieu, 35042 Rennes, France
Received 6 November 2002; received in revised form 6 November 2002; accepted 6 November 2002
Abstract
Several ruthenium(II) mono(acetylides) trans-[Cl(dppe)2RuÃ
[(dppe)2Ru(Ã(CÅC)2ÃR)2] (RꢀSiMe3, H) were selectively obtained and could be used as a new set of building blocks for rigid rod-
like structures and further assemblies. Especially, the oxidative coupling of trans-[Cl(dppe)2RuÃ(CÅC)3ÃH] with Cu(OAc)2 led to
/
(CÅ
/
C)n Ã
/
R] (nꢀ
/
1Á
/
4; Rꢀ
/
SiMe3, H) and bis(acetylide) trans-
/
/
/
/
/
/
/
the formation of the first Ruthenium(II) binuclear species with 12 carbon atoms between the remote metals. This compound shows
two reversible redox processes.
# 2002 Elsevier Science B.V. All rights reserved.
Keywords: Acetylide; Bimetallic complexes; Bridging ligand; Poly-ynes; Ruthenium complexes
1. Introduction
combination of multiples acetylides moieties or by
reaction with cumulenic species.
The chemistry of metal complexes containing alkynyl
and higher poly-ynyl ligands is now well established [1].
This metal acetylide linkage has proven to be useful to
obtain carbon rich complexes with an extended p-
conjugation. They are of interest in organic synthesis,
Previous studies showed that dppe (1,2-bis(dipheny-
phosphino)ethane) is an excellent ligand to stabilize
carbon rich species such as allenylidenes trans-
[Cl(dppe)2RuÄ
/
CÄ
/
CÄ
/
CR1R2]ꢁ and acetylides trans-
R]. For steric and electronic rea-
[Cl(dppe)2RuÃ
/
CÅ
/
CÃ
/
sons, the bulky ruthenium [RuCl(dppe)2]ꢁ moiety
protects Ca from nucleophilic attack [12,13]. We pre-
viously reported new bimetallic complexes using the new
to achieve metal cumulenylidenes [M]Ä
/
(C)n Ä/CR1R2 [2],
and to prepare liquid crystals [3], metal containing
polymers [4], supramolecular architectures [5], molecu-
lar switches [6], ONL active [7] or luminescent [8]
materials. Their contribution is also essential for the
building of molecular wires constituted of bimetallic
complexes allowing through bridge exchange of electron
trans-[ClRu(dppe)2Ã
/
CÅ
/
CÃ
/
CÅ
/
CÃ/SiMe3] acetylide as a
precursor [9,10]. Also, a Ru(II) containing bis(acetylide)
bridge has been found to enhance the ground state
electronic communication between terminal ferrocenyl
groups [14]. Therefore, the synthesis of mono and
bis(poly-yne) complexes using the [Cl2Ru(dppe)2] pre-
cursor would led, via substitution of one or two chlorine
atoms, to a new set of building blocks for rigid rod-like
between the remote metals [9Á11]. The design of later
/
motivate the selective easy to perform synthesis of new
alkynyl and bis(alkynyl) metal complexes. Indeed, one
can imagine many potential of expansion especially with
the creation of new molecular models obtained by
structure such as oligometallaynes ([M]Ã(CÅC)nꢂ
[15]. We wish now to fully account our synthetic work
)
mꢂ
[M]
on these ruthenium mono and bis(acetylide) trans-
[Cl2ꢂnRu(dppe)2](Ã
1, 2; mꢀ1Á4), and we show how to control synthesis
and deprotection. In addition, we report homocoupling
of the mono(triyne) trans-[ClRu(dppe)2ÃCÅCÃCÅCÃ
/
(CÅ
/
C)m Ã
/
R)n (Rꢀ
/
H, SiMe3; nꢀ
/
* Corresponding authors. Tel.: ꢁ
/
33-223-235767; fax: ꢁ33-223-
/
/
/
235200
E-mail addresses: stephane.rigaut@univ-rennes1.fr (S. Rigaut),
daniel.touchard@univ-rennes1.fr (D. Touchard).
/
/
/
/
/
0022-328X/02/$ - see front matter # 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 0 2 2 - 3 2 8 X ( 0 2 ) 0 2 1 0 1 - 0

38
S. Rigaut et al. / Journal of Organometallic Chemistry 670 (2003) 37Á44
/
CÅ
/
CÃ
/
H] that lead to a new poly-yne bimetallic complex
2aÁ
/
d were obtained. They were fully characterized on
vis and HR-MS (FAB)
d was
with a C12 carbon rich bridge which is the first
ruthenium complex with such an extended structure
and furthermore with a reversible redox behaviour. To
date, only three main systems were reported bearing
such a long sp carbon chain spanning two metals,
FeC12Fe [16], PtC12Pt [17], and ReC12Re 11f. The
bridge of the platinum and the rhenium species were,
respectively extended up to C16 and C20 successfully.
The rhenium system was the only one electrochemically
studied, and it did not show two distinct reversible redox
the basis of their NMR, IR, UVÁ
/
data. The trans structure of complexes 2aÁ
/
evidenced by 31P-NMR showing a singlet for the four
equivalent phosphorus nuclei. The carbon chain was
identified via 13C-NMR showing the presence of singlets
for all the Csp carbons, excepted the carbon bonded to
the metal, when observed, that shows a quintet (2JPC
15 Hz) at lower field. In the 1H-NMR spectra, the
presence of a singlet (d :0 ppm) confirmed the presence
of the trimethylsilyl group. The infrared spectroscopy
also showed characteristic triple bond vibrations be-
tween 2175 and 1970 cmꢂ1
ꢀ
/
/
systems for n ꢀ6.
/
.
The deprotection procedure of complexes 2aÁd led to
/
the isolation of a terminal acetylide complex only in the
case of 2b and 2c. The protected acetylide complexes
were dissolved in dry THF and 1.2 equivalents of
Bu4NF (1 M in THF) was added. After 1 h at room
temperature, the solvent was evaporated and the residue
purified by column chromatography on neutral alumina
to yield to 3b (95%) or 3c (90%). The structures of
2. Results and discussion
Recently, ruthenium poly-ynes have been studied by
us and others [1c,12,18] as stable redox systems. Inter-
estingly, only few protected or terminal acetylides
[RuLx](Ã
available such as the [CpRu(PPh3)2](Ã
[19] (RꢀH, SiMe3; nꢀ1), [Ru(CO)2(PEt3)2](Ã
CÅCÃR)n [20] (RꢀH, SiMe3; nꢀ2), and
[Cl2ꢂnRu(dppm)2](ÃCÅCÃCÅCÃR)n (RꢀSiMe3; nꢀ
/
CÅ
/
CÃ
/
CÅ
/
CÃ
/
R)n (Rꢀ
/
H, SiMe3; nꢀ
/
1, 2) are
CÃR)n
CÅCÃ
/
CÅCÃCÅ
/
/
/
/
complexes 3bÁc were fully determined. The disappear-
/
/
/
/
/
/
/
/
/
/
ance of the trimethylsilyl group in NMR spectroscopy,
the appearance of a signal for the terminal hydrogen
(1H-NMR), and a new signal for the corresponding
terminal carbon atom (13C-NMR) are the most striking
features. Concerning 2a, a treatment with a large excess
of Bu4NF failed to remove the silyl group, as well as the
use of a methanolic solution of KOH or K2CO3. Two
reasons can be proposed to account for this unexpected
behaviour: (i) the steric hindrance of the [(dppe)2-
RuCl]ꢁ moiety; and (ii) a higher vinylidene character
of 2a owing to the donor effect of the dppe ligands (the
/
/
/
/
/
/
/
1, 2) [21] moieties. The new protected mono-acetylide
ruthenium complexes we describe here were formed
using the classical reaction of preformed poly-yne
reagents with metal centres, and more specifically of
the poly-yne anions Li(CÅ
/
C)nSiMe3 with the metal
halide complex cis-[RuCl2(dppe)2] (1). Bis-substitution
was selectively obtained on deprotonation of the vinyl-
idene intermediates from 1-alkynes and 1 in the presence
of a non-coordinating salt and a base.
chemical shift for Ca in 13C-NMR is dꢀ
2a and dꢀ123.17 for 3b). It is worth mentioning that 3a
was previously obtained starting directly from HÃCÅ
CÃSiMe3 or from acetylene and complex 1 [24].
/
146.89 ppm for
/
2.1. Ruthenium mono-acetylide complexes
/
/
/
The pale yellow acetylide ruthenium complexes trans-
Deprotonation of the vinilydene intermediate 4 obtained
then led to 3a (Scheme 2) showing that desilylation takes
place before the acetylide formation likely via an
activated h2-complex.
[Cl(dppe)2RuÃ
achieved via addition of a slight excess (1.5 equivalents)
of the suitable lithium-acetylide LiÃ(CÅC)Ã/nSiMe3,
previously obtained by slow addition of MeLi (1.6 M
in Et2O) to Me3SiÃ(CÅC)n ÃSiMe3 in THF at ꢂ78 8C,
to suspension of 1 in THF (Scheme 1). The mixture was
stirred for 18 h at room temperature. After purification
through neutral alumina, the pure acetylide complexes
/
(CÅ
/
C)n Ã
/
SiMe3] (2aÁ
/
d) (nꢀ
/
1Á
/
4) were
/
/
It is also of note that either the mono-substitution
/
/
/
/
with HÃ
/
(CÅ
/
C)2Ã/SiMe3, in the presence of a non-
coordinating salt, or the protonation of the resulting
ruthenium diyne 2b did not lead to the vinylidene
Scheme 1. Synthesis of acetylides 2aÁ
/
d and 3bÁc.
/

S. Rigaut et al. / Journal of Organometallic Chemistry 670 (2003) 37Á
/
44
39
Scheme 2. Alternative synthesis of complex 3a.
complex trans-[Cl(dppe)2RuÄ
nor to the isolation of trans-[Cl(dppe)2RuÄ
CH2]ꢁ. We observed that when the diyne complex 2b
reacted with a strong acid such as HBF4×Et2O in
methylene chloride, a blue colour appeared before the
solution turned rapidly to orange. The orange product
was identified as the vinylidene 5b (Scheme 3). A
vinylidene characteristic vibration stretch was observed
at 1567 cmꢂ1 in the IR spectra. The 1H-NMR spectrum
/
CÄ
/
C(H)Ã
/
CÅ
/
CÃ
/
SiMe3]ꢁ
CÄCÄ
ruthenium diynes such as trans-[ClRu(dppe)2Ã
/
CÅ
/
CÃ
/
CÅCÃPh] [22] or [CpRu(PPh3)2ÃCÅCÃCÅCÃH] [19]
/
/
/
/
/
/
/
/
CÄ
/
/
/
led to the same results and conclusions especially
concerning a butatrienylidene species. So far, this kind
of intermediate has been isolated only with a complex of
iridium [23].
/
2.2. Ruthenium bis-acetylides complexes
showed up the vinylidene proton as a quintet (dꢀ
/
3.49
2.5 Hz) and the 13C-NMR spectrum, the
Attempt to perform the double substitution of the two
chlorine atoms using the poly-ynyl lithium derivatives in
order to obtain Ru(II) contening trans-bis(acetylide)
ligands were unsuccessful, even using a large amount of
the anion. We have then applied another strategy, i.e.
the deprotonation of the vinylidene intermediates ob-
tained from 1-alkyne and 1 in the presence of a non-
coordinating salt.
4
ppm, JPH
ꢀ
/
2
340.4 ppm, JPC
low field quintet for Ca (dꢀ
/
ꢀ13 Hz).
/
This reaction can be explained via protonation and
desilylation forming the blue cumulene intermediate [A].
The following addition of residual water on the electro-
philic carbon lead to 5b. The analogue vinylidene 5a was
obtained by direct addition of HÃ
/
(CÅ
/
C)2Ã
/
SiMe3 on 1 in
the presence of NaPF6. The non-coordinating salt
allows the formation of the 16 electron species which
activates the terminal alkyne certainly to also form [A],
via proton migration, before adding water. Deprotona-
This procedure, previously described to obtain 7a [24],
was successful to produce 7b (Scheme 4). The precursor
1 was reacted with four equivalents of HÃ
/
(CÅ
/
C)2Ã
/
SiMe3 in the presence of NaPF6 and Et3N in CH2Cl2.
After purification by column chromatography 7b was
obtained in good yield (77%). The 31P-NMR spectra
tions of both vinylidenes 5aÁ
/
b were easily carried out in
the presence of DBU in methylene chloride, and led to
the sole complex 6. The typical IR absorption n(CÅ
/
C)
was observed at 2001 cmꢂ1 and also n(CO) at 1603
shows a singlet at dꢀ53.57 ppm proving the trans
/
position of the two carbon chains. In the 1H-NMR
spectrum, we observe the presence of two equivalent
cmꢂ1. Characteristic 13C-NMR chemical shifts for the
2
153.5 ppm, JPC
Ca (dꢀ
/
ꢀ
/
15 Hz) and CO (dꢀ180.6
/
trimethylsilyl groups at dꢀ
/
0.21 ppm, and finally, the
ppm) were observed. Previous attempts to protonate
symmetric structure of 7b is proved by the presence of
Scheme 3. Synthesis of complex 6 via a butatrienylidene intermediate.

40
S. Rigaut et al. / Journal of Organometallic Chemistry 670 (2003) 37Á44
/
Scheme 4. Synthesis of bis(acetylides) 7aÁb and 8b.
/
only four signals for the four pairs of carbon atoms of
the two chains.
actions are the result of an odd reactivity of 2b and 3b
involving butatrienylidene intermediates (vide infra).
Thus, attempts to make use of the triyne 3c were
undertaken in order to possibly reach a binuclear
complex with 12 conjugated carbons. Only a limited
number of complexes with a C12 chain have been
described so far, FeC12Fe [16], PtC12Pt [17], and
ReC12Re [11f]. One route to obtain such compounds is
the symmetric oxidative coupling of terminal or pro-
tected acetylides. In the case of the diyne 3b, several
methods such as Eglinton or Hay coupling appeared to
by unsuccessful to obtain a C8 bridge. By contrast,
under the conditions of the Eglinton recipe (Cu(OAc)2,
pyridine, DBU), the diyne 3c reacted to form the poorly
soluble bimetallic compound 9 with 12 carbon atoms
between the remote metals (Scheme 6). This complex
was isolated as a thermally stable powder and char-
acterized on the basis of its 1H- and 31P-NMR (one
As observed for the mono(acetylide) 2a, complex 7a
could not be desilylated, probably for the same reasons.
Meanwhile, 8a was previously obtained by another
method using tributyl stannyl acetylide [24] (Scheme
5). In contrast, the bis(diyne) complex 8b could be
obtained by the simple action of Bu4NF on 7b, under
the conditions used for the formation of 3b (Scheme 4).
The structures was identified in particular with the
disappearance of the trimethylsilyl group and the
appearance of a signal for the terminal hydrogen (1H-
NMR). As the resulting complex is poorly soluble and
of limited stability, 13C-NMR could not be obtained.
2.3. Coupling of acetylide ligands: preparation of carbon-
rich bridged bimetallic complexes
singlet dꢀ
/
47.58 ppm), IR (three CÅ
/
C vibration band at
2113, 2053, and 1946 cmꢂ1), HR-MS (FAB) data. These
spectroscopic data confirmed the acetylide form of the
complex rater than the mesomeric cumulenic form. Due
to the low solubility, the 13C-NMR spectra could not be
obtained and all attempts to obtain crystals have been
unsuccessful.
Metal acetylides are potential building blocks for
further assemblies such as bimetallic molecular wire or
oligometallaynes. Indeed, novel interesting binuclear
ꢀ
ꢁ
complexes trans-[Cl(dppe)2RuÄCÄCÄCÃCHÄC(CH2)Ã
CÅCÃ(dppe)2RuCl]PF6 [9] and trans-[Cl(dppe)2RuÄCÄ
CÄC(R2)ÃC(R1)ÄC(CH3)ÃCÅCÃ(dppe)2RuCl]BF4 [10]
/
/
/
/
/
/
/
/
/
/
The RuC12Ru complex 9 bears two redox active end
groups. Cyclic voltametry analysis shows two successive
reversible oxidation waves corresponding to the radical
cation RuC12Ruꢁ and the dication RuC12Ruꢁꢁ. No
reductions were observed prior to solvent limits. The
first oxidation was observed at Eꢀ1 ꢀꢂ0:05 V versus
ferrocene and the second one at Eꢀ2 ꢀ0:18 V versus
ferrocene. The split of the two oxidations (230 mV)
show a substantial coupling between the metal centres
with seven conjugated carbons between the remote
ruthenium moieties were recently built using 2b or 3b.
The precursor was reacted, respectively with [FeCp2]PF6
as an oxidant or associated with a selected allenylidene
trans-[Cl(dppe)2RuÄ
/
CÄ
/
CÄ/C(CH2R1)R2]BF4. These re-
(Kcꢀ
/
exp(DE8F/RT)ꢀ
/
104) [11a] as the oxidations
should present high metal character. It is noteworthy
that the first oxidation is much easier that the oxidation
of an alkynyl ruthenium (E8ꢀ
2b). This result is certainly attributable to the delocalisa-
/
0.13 V vs. ferrocene for
Scheme 5. Alternative synthesis of complex 8a.
Scheme 6. Synthesis of the bimetallic RuC12Ru 9.

S. Rigaut et al. / Journal of Organometallic Chemistry 670 (2003) 37Á
/
44
41
tion of the charge on both metals. For comparison,
Gladysz’s group [11f] found for (C5Me5)Re(NO)-
(r.t.). This solution was then added to a suspension of
cis-(dppe)2RuCl2 in THF. The reaction medium was
stirred overnight at r.t. After filtration the solvent was
removed in vacuo. The crude product was washed with
(PPh3)Ã
of 190 mV for the two poorly reversible oxidation
processes (Kcꢀ1.7ꢃ
103). In our case, The larger
/
(CÅ
/
C)6Ã/(PPh3)(NO)Re(C5Me5) a separation
/
/
C5H12, dissolved in a mixture of THFÁCH2Cl2 (50/50),
/
separation of the redox processes is attributable to a
higher resonance energy or Coulombic repulsion and/or
a higher structural distortion associated with the intro-
duction of the second charge. The singly oxidized
compounds (mixed valence) should then be stable and
possible to isolate for further studies.
and purified via column chromatography (Al2O3, Et2O
as eluant).
4.1.1. trans-[Cl(dppe)2RuÃ
The general procedure with 1 ml of MeLi (1.6 mmol),
500 mg of Me3SiÃCÅCÃSiMe3 (3 mmol) in 20 ml of dry
/
CÅ
/
CÃ
/
SiMe3] (2a)
/
/
/
THF and 968 mg of 1 (1 mmol) in 40 ml of THF led to
720 mg of complex 2a (70% yield). 31P{1H}-NMR
(CDCl3): d 52.43 (s., PPh2). 1H-NMR (CDCl3): d
3. Conclusion
8.09Á
PCH2CH2P), ꢂ
/
6.81 (40H, Ph), 2.73 and 2.59 (m., 8H,
0.08 (s., 9H, SiMe3). 13C {1H}-NMR
A rational synthesis has been developed to obtain
ruthenium terminal but also protected mono-acetylides
and bis(acetylides). These systems offer potential to
reach valuable models for new one dimensional wire like
arrangements. Especially, the first ruthenium binuclear
complex with a C12 bridge showing a reversible redox
behaviour was obtained. Further investigations will lead
to novel surprising and exciting compounds with
extended carbon network especially using bis(acety-
lides).
/
2
(CDCl3): d 146.89 (quint., RuÃ
/
C Å
CÅ
24 Hz), 1.30 (s., SiMe3). IR
/
C, JPC
ꢀ14 Hz),
/
138.12Á
/
127.05 (Ph), 120.07 (s., RuÃ
/
/C), 31.08 (quint.,
PCH2CH2P, j JPCꢁ3
/
JPcjꢀ
/
1
(cmꢂ1, KBr): 1991.3 (nCÅC). HRMS-FABꢁ (m/z):
1030.1929 ([M]ꢁ, Calc.: 1030.1925). Anal. Found for
C57H57ClP4RuSi: C, 66.80; H, 5.70. Calc.: C, 66.43; H,
5.57%.
4.1.2. trans-[Cl(dppe)2RuÃ
The general procedure with 1.875 ml of MeLi (3
CÅCÃCÅCÃSiMe3 (3.4
/
CÅ
/
CÃ
/
CÅ
/
CÃ
/
SiMe3] (2b)
mmol), 660 mg of Me3SiÃ
mmol) in 40 ml of dry THF and 1.936 g of 1 (2 mmol)
/
/
/
/
/
4. Experimental
in 60 ml of THF led to 1.266 g of complex 2b (60%
1
The reactions were carried out under an inert atmo-
sphere using the Schlenk techniques. Solvents were
freshly distilled under Ar using standard procedures.
Chromatography and filtration were performed using
yield). 31P{1H}-NMR (CDCl3): d 49.09 (s., PPh2). H-
NMR (CDCl3): d 7.46Á
PCH2CH2P), 0.19 (s., 9H, SiMe3). 13C{1H}-NMR
(CDCl3): d 133.56Á127.12 (Ph, RuÃC ÅC masked by
the phenyls), 96.27 (s., RuÃCÅC), 95.53 (s., RuÃCÅCÃ
CÅCÃCÅC), 30.67 (quint.,
JPCjꢀ23 Hz), 0.02 (s., Si(CH3)3.
/6.97 (40H, Ph), 2.65 (m., 8H,
/
/
/
alumina (Acros activated neutral 50Á
/
200 mm). The
/
/
/
/
/
electrochemical studies were carried out under Ar using
an Eco Chemie Autolab PGSTAT 30 potentiostat for
cyclic voltammetry with the three-electrode configura-
tion: the working electrode was a Pt disk, the reference
electrode a saturated calomel electrode and the counter
electrode a Pt wire. Ferrocene was used as an internal
reference and the measurements were carried out in
CH2Cl2 solution with 0.1 M Bu4NPF6 as a supporting
electrolyte. Mass spectra were recorded on a Zab
SpecETOF FABꢁ spectrometer. Elemental analyses
were determined at the Villeurbanne CNRS service
central d’analyses. The precursors, cis-[(dppe)2RuCl2]
C Å
/
C), 66.83 (s., RuÃ
/
/
/
/
PCH2CH2P, j JPCꢁ3
/
/
1
IR (cmꢂ1, KBr): 2175 (m), 2103 (s) and 1999 (m) (nCÅC).
HR-MSFABꢁ (m/z): 1054.1916 ([M]ꢁ, Calc.:
1054.1925). Anal. Found for C59H57ClP4SiRu: C,
67.08; H, 5.50. Calc.: C, 67.20; H, 5.45%.
4.1.3. trans-[Cl(dppe)2RuÃ
(2c)
The general procedure with 2.53 ml of MeLi (4.05
SiMe3 (4.6
/
CÅ
/
CÃ
/
CÅ
/
CÃ
/
CÅ
/
CÃ/SiMe3]
mmol), 1 g of Me3SiÃ
/
CÅ
/
CÃ
/
CÅ
/
CÃ
/
CÅ
/
CÃ
/
mmol) in 95 ml of THF and 2.60 g of 1 (2.69 mmol)
in 80 ml of THF led to 1.16 g of complex 2c (40% yield).
[25], Me3SiÃ
[27], HÃ(CÅ
viously reported.
/
(CÅ
/
C)3Ã
/
SiMe3 [26], Me3SiÃ
/
(CÅ
/
C)4Ã
/
SiMe3
1
/
/
C)3Ã
/
SiMe3 [11f] were prepared as pre-
31P{1H}-NMR (CDCl3): d 48.36 (s., PPh2). H-NMR
(CDCl3): d 7.46Á
PCH2CH2P), 0.21 (s., 9H, SiMe3). 13C{1H}-NMR
(CDCl3): d 133.56Á127.20 (Ph, RuÃC ÅC masked by
the phenyls), 94.86 (s., RuÃCÅC), 92.34 (s., RuÃCÅCÃ
C ÅC), 76.95 (s., RuÃCÅCÃCÅC), 68.34 (s., RuÃ(CÅ
(CÅC)2ÃCÅC), 30.52 (quint.,
JPCjꢀ23 Hz), 0.37 (s., SiMe3). IR
/
6.96 (40H, Ph), 2.64 (m., 8H,
4.1. General procedure for complexes 2aÁ
/
d
/
/
/
/
/
/
/
/
A 1.6 M commercial solution of MeLi in Et2O was
added dropwise to a cooled solution (ꢂ78 8C) of
Me3SiÃ(CÅC)Ã/nSiMe3 in THF. The solution was stirred
for 1 h at ꢂ78 8C and then 2 h at room temperature
/
/
/
/
/
/
/
/
C)2Ã
/
C Å
/
C), 47.25 (s., RuÃ
/
/
/
/
1
/
/
PCH2CH2P, j JPCꢁ3
/
/
/
(cmꢂ1, KBr): 2113 (s) and 1973 (s) (nCÅC). Anal. Found

42
S. Rigaut et al. / Journal of Organometallic Chemistry 670 (2003) 37Á44
/
for C61H57ClP4SiRu: C, 68.00; H, 5.39. Calc.: C, 67.93;
H, 5.33%.
4.3. Preparation of trans-[(dppe)2(Cl)RuÄ
/
CÄ
/
CH(CO)CH3] [PF6] (5a)
A solution of 245 mg of HÃ
/
CÅ
/
CÃ
/
CÅ
/
CÃ
/
SiMe3 (2
4.1.4. trans-[Cl(dppe)2RuÃ
SiMe3] (2d)
The general procedure with 1.1 ml of MeLi (1.76
mmol), 485 mg of Me3SiÃ(CÅC)4ÃSiMe3 (2.0 mmol) in
/
CÅ
/
CÃ
/
CÅ
/
CÃ
/
CÅ
/
CÃ
/
CÅ
/
CÃ
/
mmol) in 100 ml of CH2Cl2 was added to 968 mg of 1 (1
mmol) and 360 mg of NaPF6 (2 mmol). The mixture was
stirred for 24 h at r.t. After filtration of the solution,
evaporation of the solvent, the residue was washed with
/
/
/
40 ml of THF and 1.14 g of 1 (1.18 mmol) in 40 ml of
THF led to 265 mg of complex 2d (20% yield). 31P{1H}-
NMR (CDCl3): d 47.58 (s., PPh2). 1H-NMR (CDCl3): d
Et2O. Crystallisation in a CH2Cl2ÁC5H12 mixture led to
/
1.03 g of 5a (90% yield). 31P{1H}-NMR (CD2Cl2): d
1
711 Hz, PF6). H-
41.27 (s., PPh2), ꢂ
/
144.1 (sept., JPF
ꢀ
/
7.47Á
(s., 9H, SiMe3). 13C{1H}-NMR (CDCl3): d 135.49Á
C masked by the phenyls), 94.80,
/7.00 (40H, Ph), 2.64 (m., 8H, PCH2CH2P), 0.19
NMR (CD2Cl2): d 7.50Á
/
7.08 (40H, Ph), 3.39 (quint.,
CH), 2.87 (m., 8H,
4
1H, JPH
/
ꢀ
/
2.3 Hz, RuÄ
/
CÄ
/
PCH2CH2P), 1.45 (s., 3H, CH3). 13C{1H}-NMR
127.70 (Ph, RuÃ
/
C Å
/
2
(CD2Cl2): d 340.43 (quint., JPC
90.70, 82.12, 77.61, 67.64, 54.98 and 48.08 (CÅ
/
C), 30.66
ꢀ
/
12 Hz, RuÄ
/
C),
(quint., PCH2CH2P, j JPCꢁ3
/
JPCjꢀ
/
23 Hz), 0.34 (s.,
1
191.47 (s., CO), 134.27Á
/
128.17 (Ph), 112.61 (s., RuÄ
/
SiMe3). IR (cmꢂ1, KBr): 2104, 2070, 2039 and 1963
(s) (nCÅC). Anal. Found for C63H57ClP4SiRu: C, 68.19;
H, 5.01. Calc.: C, 68.62; H, 5.21%.
1
CÄ
/
C), 30.04 (s., CH3), 29.22 (quint., j JPCꢁ3
/
JPCjꢀ
/
23
Hz, PCH2CH2P). IR (cmꢂ1, KBr): 1570 (nCÄC), 738
(nPF). Anal. Found for C56H52ClF6OP5Ru: C, 58.95; H,
4.71. Calc.: C, 58.67; H, 4.57%.
4.2. General procedure for complexes 3bÁc
/
4.4. Preparation of trans-[(dppe)2(Cl)RuÄ
/
CÄ
/
CH(CO)CH3] [BF4] (5b)
In a Schlenk tube containing complex 2 dissolved in
THF, 1.1 equivalent of a commercial solution of Bu4NF
(1 M in THF) was added. The reaction medium was
stirred for 1 h. After solvent evaporation the residue was
washed with water, dried and washed with C5H12.
To a solution of 527 mg of 2b (0.5 mmol) in 50 ml of
Et2O in Et2O was
added. After 1 h at r.t., the solvent was evaporated and
CH2Cl2, 90 ml of a solution of HBF4×
/
the residue washed with Et2O. Crystallisation in a
CH2Cl2ÁC5H12 mixture led to 473 mg of 5b (87% yield).
/
31P{1H}-NMR (CDCl3): d 41.15 (s., PPh2). H-NMR
1
4.2.1. trans-[Cl(dppe)2RuÃ
/
(CÅ
/
C)2Ã
/
H] (3b)
4
(CDCl3): d 7.42Á
Hz, RuÄCÄ
3H, CH3). 13C{1H}-NMR (CDCl3): d 340.42 (quint.,
2JPC
13 Hz, RuꢀC), 191.23 (s., CO), 134.27Á128.16
CÄC), 30.03 (s., CH3), 29.21
23 Hz, PCH2CH2P). IR (cmꢂ1
/6.99 (Ph), 3.49 (quint., 1H, JPH
ꢀ2.5
/
The general procedure with 1.05 g of 2b in 50 ml of
THF (1 mmol) 1.1 ml of Bu4NF (1.1 mmol) led to 0.88 g
/
/
CH), 2.85 (m., 8H, PCH2CH2P), 1.43 (s.,
of 3b (95% yield). 31P{1H}-NMR (CDCl3): d 49.00 (s.,
1
ꢀ
/
/
/
PPh2). H-NMR (CDCl3): d 7.46Á
/
6.99 (40H, Ph), 2.66
CÃ
H). 13C{1H}-
127.12 (Ph), 123.17 (quint.,
), 94.46 (s., RuÃCÅC), 74.51 (s.,
), 50.89 (s., RuÃCÅCÃCÅC), 30.57
23 Hz, PCH2CH2P). IR (cmꢂ1
,
(Ph), 112.61 (s., RuÄ
/
/
(m., 8H, PCH2CH2P), 1.28 (s., 1H, Å
NMR (CDCl3): d 135.61Á
2JPC
16 Hz, RuÃC Å
/
/
1
(quint., j JPCꢁ3
/
JPCjꢀ
/
,
/
KBr): 1567 (nCÄC). Anal. Found for C56H52ClF4OP4Ru:
C, 62.01; H, 4.87. Calc.: C, 61.81; H, 4.82%. HR-
MSFABꢁ (m/z): 1001.1718 ([Mꢁ], Calc. 1001.1713).
ꢀ
/
/
/
/
/
RuÃ
/
CÅ
/
CÃ
/
C Å
/
/
/
/
/
(quint., j JPCꢁ3
/
JPCjꢀ
/
1
KBr): 3264 (nCH), 2102 (nCÅC). Anal. Found for
C56H49ClP4Ru: C, 68.76; H, 4.97. Calc.: C, 68.47; H,
5.03%.
4.5. Preparation of trans-[(dppe)2(Cl)RuÃ
/
CÅ
/
CÃ
/
(CO)ÃCH3] (6)
/
To a solution of 1.15 g of 5a (1.00 mmol) in 100 ml of
CH2Cl2, 598 ml of DBU (4.00 mmol) was added. After 1
h at r.t. and evaporation of the solvent, the residue was
washed with C5H12, dissolved in THF, and purified by
column chromatography (Al2O3, Et2O as solvent).
4.2.2. trans-[Cl(dppe)2RuÃ
/
(CÅ
/
C)3Ã
/
H] (3c)
The general procedure with 1.08 g of 2c in 75 ml of
THF (1 mmol) of Bu4NF (1.1 mmol) led to 0.9 g of
complex 3c (90% yield). 31P{1H}-NMR (CDCl3): d
1
48.88 (s., PPh2). H-NMR (CDCl3): d 7.37Á
/
6.93 (40H,
CH).
127.05 (Ph, RuÃC Å
Crystallisation in a CH2Cl2ÁC5H12 mixture led to 800
/
Ph), 2.57 (m., 8H, PCH2CH2P), 1.68 (s., 1H, Å
/
mg of 6 (80% yield). 31P{1H}-NMR (CDCl3): d 48.65
1
13C{1H}-NMR (CDCl3): d 135.16Á
/
/
/
(s., PPh2). H-NMR (CDCl3): d 7.46Á
/
6.99 (40H, Ph),
2.72 (m., 8H, PCH2CH2P), 1.54 (s., CH3). 13C{1H}-
NMR (CDCl3): d 180.66 (s., CO), 153.52 (quint.,
masked by the phenyls), 94.27, 72.34, 66.69, 59.62,
59.11, 30.52 (quint., PCH2CH2P, j JPCꢁ3
/
JPCjꢀ
/
23
1
Hz). IR (cmꢂ1, KBr): 3295 (nCH); 2132, 2079 and
1964 (nCÅC). Anal. Found for C58H49ClP4Ru: C, 68.81;
H, 4.77. Calc.: C, 69.22; H, 4.91%.
2JPC
ꢀ
/
15 Hz, RuÃ
CÅC), 31.84 (s., CH3), 30.91 (quint.,
JPCjꢀ
22 Hz, PCH2CH2P). IR (cmꢂ1, KBr):
/
C Å
/
C), 136.13Á
/
127.66 (Ph), 120.94
(s., RuÃ
/
/
1
j JPCꢁ3
/
/

S. Rigaut et al. / Journal of Organometallic Chemistry 670 (2003) 37Á
/
44
43
2001 (nCÅC). Anal. Found for C56H51ClOP4Ru: C, 66.87;
H, 4.96. Calc.: C, 67.23; H, 5.14%.
Acknowledgements
We thank the CNRS and the universite´ de Rennes 1
for support, Dr P. Gue´not from the Centre Re´gional de
Mesures Physiques de l’Ouest (Rennes) for assistance in
structure determination.
4.6. Preparation of trans-[(dppe)2RuÃ
/
(CÅ
/
CÃ
/
CÅ
/
CÃ
/
SiMe3)2] (7b)
In a Schlenk tube containing 775 mg of 1 (0.80 mmol)
and 537 mg (3.20 mmol) of NaPF6, a solution of HÃCÅ
CÃCÅCÃSiMe3 (3.20 mmol), 800 ml (6.40 mmol), and
/
/
/
/
/
References
100 ml of CH2Cl2 was added. After 22 h at r.t., the
solution was filtered and the solvent evaporated. The
residue was washed with C5H12. After purification by
column chromatograpy on neutral alumina, eluted with
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2
(quint., JPC
ꢀ
/
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/
C Å
/
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/
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/
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/
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/
/
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/
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CH3). IR (cmꢂ1, KBr): 2166 (m), 2109 (s) and 1993 (m)
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/
(CÅ
/
CÃ
/
CÅ
/
CÃ
/
(b) S.K. Hurst, M.G. Humphrey, T. Isoshima, K. Wostyn, I.
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H)2] (8b)
In a Schlenk tube containing 114 mg of 7a (0.1 mmol)
in 30 ml of THF, 0.3 ml (0.3 mmol) of Bu4NF (1 M in
THF) was added. The reaction medium was stirred for 2
h after evaporation, the residue was chromatographied
on neutral alumina (elution with a mixture (1:1)
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CH2Cl2Á
yield). 31P{1H}-NMR (CDCl3): d 53.50 (s., PPh2). H-
NMR (CDCl3): d 7.34Á6.96 (40H, Ph), 2.58 (m., 8H,
PCH2CH2P), 1.41 (s., 2H, CÅ
CH). IR (cmꢂ1, KBr):
2112 (s) and 1971 (m) (nCÅC).
/
Et2O), and 95 mg of 8b was obtained (94%
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/
/
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/
180, 431;
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/
(CÅ
/
C)6Ã
/
/
(c) P.F.H. Schab, M.D. Levin, J. Michl, Chem. Rev. 99 (1999)
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Copper(II) acetate (0.5 mmol) in 40 ml of Py, 75 ml of
DBU (0.5 mmol) was added. The solution was stirred
for 3 h at r.t. After evaporation of the solvent, the
residue was washed with Et2O and dried. After extrac-
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obtained (90% yield). 31P{1H}-NMR (CDCl3): d 47.58.
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/
5440;
/
/
1H-NMR (CD2Cl2): d 7.45Á
16H, PCH2CH2P). IR (cmꢂ1, KBr): 2113, 2053 and
1946 (nCÅC). HR-MSFABꢁ (m/z): 2011.2971 ([Mꢁ
H]ꢁ,
Calc. 2011.2955). Anal. Found for
116H96Cl2P8Ru2: C, 68.93; H, 4.77. Calc.: C, 69.29;
H, 4.81%.
/
6.96 (80H, Ph), 2.60 (m.,
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¨
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/
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/
/
C
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