Ruthenium and Rhodium Complexes of Thioether-Alkynylborates

The species ((C₆F₅)₂BCH₂SPh)₂ reacts with PhCCLi to give the thioether-alkynylborate (C₆F₅)₂BCH₂SPh­(CCPh)­Li­(THF)₂ (1). Subsequent reaction with (Ph₃P)₃RuHCl, (Ph₃P)₃RhCl, and [(COD)­Rh­(μ-Cl)]₂ gives (C₆F₅)₂BCH₂SPh­(CCPh)­RuH­(PPh₃)₂ (2), (C₆F₅)₂BCH₂SPh­(CCPh)­Rh­(PPh₃)₂ (4), and (C₆F₅)₂BCH₂SPh­(CCPh)­Rh­(COD) (5), respectively, demonstrating a bidentate binding mode via the alkynyl and thioether donors of the borate. Subsequent reactions of 2 and 4 with H₂ gave (C₆F₅)₂BCH₂SPh­(CH₂CH₂Ph)­RuH­(PPh₃)₂ (3) and ((C₆F₅)₂BCH₂SPh­(CHCHPh))­Rh­(PPh₃)₂ (6). In the former case, the borate remains bound to the metal via a π-interaction with the thioether-arene ring, while in the latter case, S and alkene binding is observed.