Cooperative B-H and Si-H Bond Activations by κ²-N,S-Chelated Ruthenium Borate Complexes

Cooperative E-H (E = B, Si) bond activations employing κ²-N,S-chelated ruthenium borate species, [PPh₃{κ²-N,S-(NS₂C₇H₄)}Ru{κ³-H,S,S'-H₂B(NC₇H₄S₂)₂}], (1) are established. Treatment of 1 with BH₃·SMe₂ yielded the six-membered ruthenaheterocycle [PPh₃{κ²-S,H-(BH₃NS₂C₇H₄)}Ru{κ³-H,S,S'-H₂B(C₇H₄NS₂)₂}] (2) formed by a hemilabile ring opening of a Ru-N bond and capturing of a BH₃ unit coordinated in an "end-on" fashion. On the other hand, the bulky borane H₂BMes shows different reactivity with 1 that led to the formation of the two dihydroborate complexes [{κ³-S,H,H-(NBH₂Mes)(S₂C₇H₄)}Ru{κ³-H,S,S'-H₂B(C₇H₄NS₂)₂}] (3) and [PPh₃{κ³-S,H,H-(NBH₂Mes)(S₂C₇H₄)}Ru(κ²-N,S-C₇H₄NS₂)] (4), in which H₂BMes has been inserted into the Ru-N bond of the initial κ²-N,S-chelated ligand. In an attempt to directly activate hydrosilanes by 1, reactions were carried out with H₂SiPh₂ that yielded two isomeric five-membered ruthenium silyl complexes, namely [PPh₃{κ²-S,Si-(NSiPh₂)(S₂C₇H₄)}Ru{κ³-H,S,S'-H₂B(C₇H₄NS₂)₂}] (5a,b), and the hydridotrisilyl complex [Ru(H){κ²-S,Si-(SiPh₂NC₇H₄S₂}₃] (6). These complexes were generated by Si-H bond activation with the release of H₂ and the formation of N-Si and Ru-Si bonds. When the reaction of 1 was carried out in the presence of PhSiH_3, the reaction only produced the analogous complexes [PPh₃{κ²-S,Si-(NSiPhH)(S₂C₇H₄)}Ru{κ³-H,S,S'-H₂B(C₇H₄NS₂)₂}] (5a',b'). Density functional theory (DFT) calculations have been used to probe the bonding modes of boranes/silane with the ruthenium center.