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.