4 years ago

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)

Ting-Bin Wen, Hongping Zhu, Peng Nie, Qian Yu
The reactions of MXCl(PPh3)3 (M = Ru, Os; X = H, Cl) 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 the dichlorogermyl chloro- or hydrido- ruhenium/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) via insertion of the germylene into the M-Cl bond followed by 6-coordination of one of the Trip group 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 orthometallation of the PPh3 ligand via dehydrochorination in the germylidene intermediate followed by migratory of the metallated 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 the hydrido ruthenium complex 3, while treatment of 3 with PhCH2MgCl led to the benzylation at Ge to give the hydrido ruthenium dibenzylgermyl complex (PPh3)(H)RuGe(CH2Ph)2(C6H3-2-{η6-Trip}-6-Trip) (8).

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/ejic.201700991

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