Formation of a Boraruthenacyclopentenyl Skeleton via B–C Bond Formation across a Triruthenium Plane

The treatment of a trimetallic complex containing a μ3-borylene ligand, (Cp*Ru)3(μ3-BH)­(μ-H)3 (6; Cp* = η5-C5Me5), with 1 atm of acetylene resulted in the incorporation of
two molecules of acetylene on the opposite face of the μ3-borylene ligand to form a μ3-η2(∥)-ethyne μ-ethylidene complex, (Cp*Ru)3(μ3-BH)­(μ3-η2(∥)-HCCH)­(μ-CHCH3)­(μ-H) (7a). Although an intermediate was not observed in the reaction of 6 with acetylene, the intermediary monoalkyne complex 8b was obtained by the reaction of 6 with phenylacetylene,
which was converted into (Cp*Ru)3(μ3-BH)­(μ3-η2(∥)-PhCCH)­(μ-CHCH3)­(μ-H) (7b) upon subsequent reaction with acetylene.
The thermolysis of 7a provided a closo-2-boraruthenacyclopentenyl complex, {Cp*Ru­(μ-H)}2{Cp*Ru­(−BHCHCMeCH−)} (11), as a consequence
of B–C bond formation across the Ru3 plane with
the partial breakage of the cluster skeleton. An X-ray diffraction
study for 11 clearly showed the formation of a boraruthenacyclopentenyl
skeleton, which bisects the triruthenium plane. This transformation
shows how important the flexibility of cluster skeleton is for the
bond-forming reaction.