Formation of μ-peroxo-platinum complexes via attack of metallic and related electrophiles at η2-dioxygen-platinum complexes
作者:Hideo Kurosawa、Toshio Achiha、Hiroshi Kajimaru、Isao Ikeda
DOI:10.1016/s0020-1693(00)80264-9
日期:1991.12
Reactions of PtO2(PPh3)2 with metallic chlorides or related chlorides LnMCl in CD2Cl2 at -40-degrees-C gave good yields of the corresponding mu-peroxo complexes Pt(OOMLn)(Cl)(PPh3)2 (2) (LnM = Me3Si, Ph3Si, Ph3Ge, Ph2P(O), (PhO)2P(O), PhS(O)2 which were confirmed by P-31 NMR measurements. In P-31 NMR data of 2, the J(Pt-P) values for PPh3 trans to OOMLn increased as the electron-withdrawing ability of LnM increased, whereas the J(Pt-P) values for PPh3 cis to OOMLn showed somewhat unusual inverse linear dependency on this ability. Treatment of PtO2(PR3)2 with [Pt2(mu-OH)2(PR'3)4]2+ afforded mu-peroxo-diplatinum complexes [(PR3)2Pt(mu-OO)(mu-OH)Pt(PR'3)2]+ (R = R' = Ph, p-tolyl; PR3 = PPh3; PR'3 = PMe2Ph, 1/2Ph2PCH2CH2PPh2). Complexes 2 containing electron-withdrawing peroxo ligands (LnM = Ph2P(O), (PhO)2P(O), PhS(O)2) oxidized norbornene and cyclohexene to the corresponding epoxides.