Ruthenium complexes with bridging functionalized alkylidene ligands. Synthesis of [Ru 2CP 2(CO) 2(μ-CO){μ-C(X)N(Me)CH 2Ph}] (X = H, CN) and molecular structure of the CN derivative

Abstract

The isocyanide complex [RU 2CP 2(CO) 3(CNCH 2Ph)], obtained by the reaction of [RU 2CP 2(CO) 4] with CNCH 2Ph in the presence of Me 3NO, has been N-alkylated, yielding the cationic μ-alkylidyne complex [Ru 2CP 2(CO) 3{μ-CN(Me)CH 2Ph}]SO 3CF 3. The compound yielded undergoes nueleophilic addition using NaBH 4 or NaBu 4CN at the μ-C alkylidyne carbon to give the novel μ-aminoalkylidene complexes [Ru 2Cp 2(CO){μ-C(X)N(Me)CH 2Ph}] (X = H, CN). The derivative with X = CN adopts the expected geometry and an idealized C s symmetry if the phenyl substituent is ignored. The relevant bond distances are as follows: RuRu, 2.711(1) Å; Ru-μ-C(carbene), 2.090(4) Å (ave.); C(carbene)-N, 1.477(5) Å; N-C(alkyl), 1.474(5) Å (ave.).