Ruthenium and Osmium Germyl Complexes Derived from the Reactions of MXCl(PPh3)3 (M = Ru, Os; X = Cl, H) with Terphenylchlorogermylene (C6H3‐2,6‐Trip2)GeCl (Trip = 2,4,6‐iPr3C6H2)

• Published in: European journal of inorganic chemistry 2017-11, Vol.2017 (40), p.4784-4796
• Main Authors: Nie, Peng, Yu, Qian, Zhu, Hongping, Wen, Ting‐Bin
• Format: Article
• Language: English
• Subjects: Germanium; Germylenes; Heterometallic complexes; Inorganic chemistry; Ligands; Osmium; Ruthenium
• ISSN: 1434-1948; 1099-0682
• DOI: 10.1002/ejic.201700991

The reactions of MXCl(PPh3)3 (M = Ru, Os; X = Cl, H) with (C6H3‐2,6‐Trip2)GeCl (Trip = 2,4,6‐iPr3C6H2) have been investigated. Teatment of MXCl(PPh3)3 with (C6H3‐2,6‐Trip2)GeCl led to the formation of dichlorogermyl chloro or hydrido ruthenium/osmium complexes (PPh3)XMGeCl2(C6H3‐2‐{η6‐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 η6‐coordination of one of the Trip groups of the terphenyl to the Ru/Os center with concomitant dissociation of PPh3 ligands. Noteworthily, the reaction on OsHCl(PPh3)3 also led to the formation of an unexpected minor product Os(H)(PPh2C6H4)GeCl(C6H3‐2‐{η6‐Trip}‐6‐Trip) (5) containing a diphenylphosphinophenyl‐germyl ligand, which is presumably formed by orthometalation of the PPh3 ligand through dehydrochorination in the germylidene intermediate followed by migration of the metalated phenyl group to germanium. Reaction of 1 with PMe3 or treatment of 1 with DMSO in the presence of CuCl as the phosphine scavenger produced the PMe3‐ or DMSO‐substituted derivatives (L)ClRuGeCl2(C6H3‐2‐{η6‐Trip}‐6‐Trip) (L = PMe3, 6; L = DMSO, 7). The reaction of 1 with LiHBEt3 afforded hydrido ruthenium complex 3, while treatment of 3 with PhCH2MgCl led to benzylation at Ge to give hydrido ruthenium–dibenzylgermyl complex (PPh3)(H)RuGe(CH2Ph)2(C6H3‐2‐{η6‐Trip}‐6‐Trip) (8). Reactions of MXCl(PPh3)3 (M = Ru, Os; X = Cl, H) with chlorogermylene (C6H3‐2,6‐Trip2)GeCl gave dichlorogermyl complexes (PPh3)XMGeCl2(C6H3‐2‐{η6‐Trip}‐6‐Trip) through insertion of the germylene into the M–Cl bonds followed by η6‐coordination of one Trip group to the Ru/Os center. The reaction on OsHCl(PPh3)3 also afforded the unexpected minor product Os(H)(PPh2C6H4)GeCl(C6H3‐2‐{η6‐Trip}‐6‐Trip).