The reactivity of the amino(cyano)borane iPr2NBH(CN) (2) towards [RuH2(η2-H2)2(PCy3)2] (3) was investigated. Our study reveals that the formation of the bis(isocyanoborane) ruthenium complex [RuH(CN)(CN-BHNiPr2)2(PCy3)2] (6) occurs via the intermediacy of the bis(σ-B–H) ruthenium complex [RuH(CN)(H2BNiPr2)(PCy3)2] (5). This transformation involves BCN linkage isomerisation in 2. The diisopropylaminoborane ligand in 5 can be displaced to ultimately produce the bis(σ-borane) complex [RuH2(η2:η2-H2BNiPr2)(PCy3)2] (4) as a by-product.
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