om950835w_si_001.pdf (1.05 MB)
Self-Activation of a Cluster-Bound Alkyne toward Carbon−Carbon Bond Forming Reactions
journal contribution
posted on 1996-02-20, 00:00 authored by Soa Rivomanana, Carole Mongin, Guy LavigneThe methanol-catalyzed elimination of Cl- from the
“activated” anionic species
[PPN][Ru3(μ-Cl)(μ-PhCCPh)(CO)9] (1) in the
presence of bis(diphenylphosphino)methane (dppm)
constitutes a rational high-yield route (>90%) to either the unique
unsaturated 46-e (alkyne)triruthenium cluster,
Ru3(μ-PhCCPh)(CO)7(dppm)
(2), or its 48-e CO adduct,
Ru3(μ-PhCCPh)(CO)8(dppm) (3). Whereas the CO-induced
conversion of 2 into 3 is complete within
few
seconds at 25 °C under 1 atm of CO, the reverse transformation takes
1 h at 80 °C. The
X-ray structure analysis of 2 is reported, revealing a
perpendicular conformation of the alkyne
relative to the metal triangle. The high reactivity of
2 is substantiated by a high chemical
reactivity toward 2-e donors. Its reaction with 1 equiv of dppm
(25 °C, 3 h) leads to the
bis-dppm-substituted complex,
Ru3(μ-PhCCPh)(CO)6(dppm)2
(4) (53% yield). Reaction of
2
with hydrogen gas (1 atm, 25 °C, 10 min) yields the dihydrido
species,
Ru3(μ-H)2(μ-PhCCPh)(CO)7(dppm) (5) (89% yield) existing as a
mixture of two isomers differing in the orientation
of the alkyne relative to the edge-bridging dppm ligand. Complex
2 reacts with a terminal
alkyne like phenylacetylene under mild conditions to afford a mixture
of the “fly-over” type
compound
Ru3{μ-HCC(Ph)C(O)(Ph)CCPh}(dppm)(CO)6
(6) (57% yield) and the diruthenacyclopentadiene derivative
Ru2{μ-HCC(Ph)(Ph)CCPh}(μ-dppm)(CO)4
(7) (20% yield). The
structure of 6 reveals the occurrence of a disymmetric
edge-bridging dialkenyl ketone ligand
HCC(Ph)C(O)(Ph)CCPh, resulting from regioselective
coupling between the two alkynes
and a carbonyl group. The formal unsaturation of 6 is
masked by a weak interaction between
the terminal C−Ph bond of the organic chain and one of the metal
centers. Facile loss of
this interaction is induced by mild thermolysis of 6.
As a consequence, free rotation of the
organic moiety around the metal−metal edge brings the opposite end of
the organic chain
(i.e., the C−H bond) close to the opposite face, thereby favoring CH
activation to convert
the alkenyl end into a vinylidene. This leads to quantitative
formation of the vinylidene
alkenyl ketone derivative,
Ru3(μ-H){μ-CC(Ph)C(O)(Ph)CCPh}(dppm)(CO)6
(8) (94% yield).
The X-ray structure of 8 is reported. Unsuccessful
attempts to release the organic moiety
from the cluster core are described. The reaction of a THF
solution of 6 with CO in a reactor
[P(CO) = 10 atm, T = 80 °C] leads to the
new binuclear “fly-over” species
Ru2{μ-HCC(Ph)C(O)(Ph)CCPh}(CO)6 (9a), thereby
indicating that elimination of the edge-bridging dppm and
cluster fragmentation are more favorable than elimination of a free
ketone from the intact
cluster. The X-ray structure of
Ru2{μ-HCC(C3H7)C(O)(Ph)CCPh}(CO)6
(9b) (resulting from
the coupling between diphenylacetylene and 1-pentyne) is reported.