Oxygen Atom Transfer Reactions from Dioxygen to Phosphines via a Bridging Sulfur Dioxide in a Trinuclear Cluster Complex of Rhenium,

摘要

A trinuclear rhenium sulfide cluster complex,[(Ph_3P)_2N][Re_3(M_3-S)(mu_3-S)_3CI_6(PMe_2Ph)_3],synthesized from Re_3S_7CI_7,dimethylphenylphosphine,and [(Ph_3P)_2N]CI is readily converted to a bridging S02 complex,[(Ph_3P)_2N][Re_3(mu_3-S)-(mu-S)_2(M-S0_2)CI_6(PMe_2Ph)_3],by reaction with 0_2.The oxygen atoms on the S0_2 ligand react with phosphines or phosphites to form phosphine oxides or phosphates,and the original cluster complex is recovered.The reaction course has been monitored by ~31P NMR as well as by UV-vis spectroscopy.The catalytic oxygenation of PMePh_2 in the presence of the S0_2 complex shows that turnovers are 8 per hour at 23 deg C in CDCI_3.The X-ray structures of the cluster complexes are described.