Ruthenium and Osmium Germyl Complexes Derived from the Reactions of MXCl(PPh 3 ) 3 (M = Ru, Os; X = Cl, H) with Terphenylchlorogermylene (C 6 H 3 ‐2,6‐Trip 2 )GeCl (Trip = 2,4,6‐ i Pr 3 C 6 H 2 )

The reactions of MXCl(PPh 3 ) 3 (M = Ru, Os; X = Cl, H) with (C 6 H 3 ‐2,6‐Trip 2 )GeCl (Trip = 2,4,6‐ i Pr 3 C 6 H 2 ) have been investigated. Teatment of MXCl(PPh 3 ) 3 with (C 6 H 3 ‐2,6‐Trip 2 )GeCl led to the formation of dichlorogermyl chloro or hydrido ruthenium/osmium complexes (PPh 3 )XMGeCl 2 (C 6 H 3 ‐2‐{η 6 ‐Trip}‐6‐Trip) (M = Ru, X = Cl, 1 ; M = Os, X = Cl, 2 ; M = Ru, X = H, 3 ; M = Os, X = H, 4 ) through insertion of the germylene into the M–Cl bond followed by η 6 ‐coordination of one of the Trip groups of the terphenyl to the Ru/Os center with concomitant dissociation of PPh 3 ligands. Noteworthily, the reaction on OsHCl(PPh 3 ) 3 also led to the formation of an unexpected minor product Os(H)(PPh 2 C 6 H 4 )GeCl(C 6 H 3 ‐2‐{η 6 ‐Trip}‐6‐Trip) ( 5 ) containing a diphenylphosphinophenyl‐germyl ligand, which is presumably formed by orthometalation of the PPh 3 ligand through dehydrochorination in the germylidene intermediate followed by migration of the metalated phenyl group to germanium. Reaction of 1 with PMe 3 or treatment of 1 with DMSO in the presence of CuCl as the phosphine scavenger produced the PMe 3 ‐ or DMSO‐substituted derivatives (L)ClRuGeCl 2 (C 6 H 3 ‐2‐{η 6 ‐Trip}‐6‐Trip) (L = PMe 3 , 6 ; L = DMSO, 7 ). The reaction of 1 with LiHBEt 3 afforded hydrido ruthenium complex 3 , while treatment of 3 with PhCH 2 MgCl led to benzylation at Ge to give hydrido ruthenium–dibenzylgermyl complex (PPh 3 )(H)RuGe(CH 2 Ph) 2 (C 6 H 3 ‐2‐{η 6 ‐Trip}‐6‐Trip) ( 8 ).