Diphenylantimony(V) oxo/chloro carboxylates and phosphinates: Crystal structures of {SbPh < inf > 2 < /inf > Cl[O < inf > 2 < /inf > P(C < inf > 6 < /inf > H < inf > 11 < /inf > ) < inf > 2 < /inf > ]} < inf > 2 < /inf > O and [SbPh < inf > 2 < /inf > (O < inf > 2 < /inf > CPh) < inf > 2 < /inf > ] < inf > 2 < /inf > O

Abstract

Reaction of SbPh2Cl3 (1 mol) with the silver salt of dicyclohexylphosphinic acid (2 mol) afforded {SbPh2Cl[O2P(C6H11) 2]}2O 1; a similar reaction with AgO2P(C8H15)2 gave a product formulated as {SbPh2Cl[O2P(C8H15) 2]}2O 2. Similar reactions with silver carboxylates (1: 3 stoichiometry) led to the crystalline derivatives [SbPh2(O2CR)2]2O (R = Ph 3, CHPh2 4, 2,4,6-Me3C6H2 5, 2-MeC6H4 6 or 4-MeC6H4 7), whereas the 1: 2 reaction afforded crystalline SbPh2Cl(O2CR)2 (R = Ph 8, 2-MeC6H4 9 or 4-MeC6H4 10). Interconversion of the previously known compounds [SbPh2(O2CMe)2]O and Sb4Ph8O6·3MeCO2H was achieved and established by 1H NMR spectroscopy. Compounds 1 and 3 were further characterized by X-ray diffraction; the antimony in 1 is six-co-ordinated with bridging phosphinates whereas in 3 it is seven-co-ordinated with chelating benzoates. Short Sb-O (oxo) distances (1.923 Å) and near linearity at the bridging oxygen (Sb-O-Sb 173.9°) are observed for 3.