Chemistry of ruthenium σ-borane complex, [Cp*RuC0(μ-H)BH2L] (Cp* = η5-C5Me5; L = C7H4NS2) with terminal and internal alkynes: Structural characterization of vinyl hydroborate and vinyl complexes of ruthenium

The chemistry of ruthenium-borane complex, [Cp*RuCO(mu-H)BH2L] (Cp* = eta(5)-C5Me5; L = C7H4NS2), 1 with various alkynes has been explored. Photolysis of 1 with allcynyl-Grignard, [HC equivalent to CMgBr] in toluene led to the isolation of vinyl hydroborate complex [Cp*Ru(mu-H)BH{HC=CH2}L], 2a as a sole product. Compound 2a can be viewed as a ruthenium-borate complex with an ethylene moiety. Further, the chemistry of 1 with various internal and terminal alkynes has been performed in photolytic conditions. Photolysis of 1 with [RC equivalent to CR] (R = CO2Me) yielded vinyl hydroborate complex [Cp*Ru(mu-H)BC1{RC=CR}L], 2b. Terminal alkynes [HC equivalent to CR] (R = Ph or CO2Me) under the same reaction conditions led to the isolation of metal vinyl complexes [Cp*Ru(CO)(C2HR)(L)1, 3a and 3b (3a: R = Ph; 3b: R = CO2Me). In addition, DFT calculations were carried out to analyze the bonding and electronic structures of these new compounds. (C) 2017 Elsevier Ltd. All rights reserved.