Dimethylphosphinato and dimethylarsinato complexes of Sb(III) and Bi(III) and their chemistry

摘要

The reaction of Me2PO2H and Me2AsO2H with SbCl3, BiCl3, and Bi(NO3)3·5H2O gave the complexes Sb(Me2PO2)3, Sb(Me2AsO2)3, (Me2PO2)2Bi-Cl, Bi(Me2-AsO2)3, (Me2PO2)2Bi(NO3), and (Me2AsO2)2Bi(NO3)-H2O, respectively. The arsinato complexes did not react with the Lewis bases pyridine, Ph3P, and Ph3As in acetone. The compounds Sb(Me2AsO2)3 and (Me2AsO2)2Bi(NO3)-H2O reacted to a small extent with nicotinic acid in methanol but Bi(Me2AsO2)3 gave (Me2AsO2-BiO)_x in good yields. (Me2AsO2)2Bi(NO3)H2O in methanol quantitatively rearranged to new complexes with the same composition, [(Me2AsO2)2Bi(NO3)·H2O]' and [(Me2AsO2)2Bi(NO3)· H2O]" in the presence of pyridine. With thiophenol in air, Sb(Me2AsO2)3 gave PhSSPh and Me2As-SPh (1:1 mol ratio), (Me2AsO2-SbO)_x and some Sb(Me2AsO2)3 was reformed, Bi(Me2AsO2)3 gave (Me2AsO2-BiO)_xPhSSPh, and Me2As-SPh (1:0.6 mol ratio), whereas (Me2AsO2)2Bi(NO3)H2O quantitatively gave PhSSPh, thus acting as a catalyst for the air oxidation of thiophenol.