Mono-, Bi-, and Trinuclear Triarylantimony Organylsulfonate Derivatives: Synthesis and Structure

Abstract

The reactions of tris(3-methylphenyl)antimony with trifluoromethanesulfonic acid and of triphenylantimony with 3,4-dimethylbenzenesulfonic acid in the presence of tert-butylhydroperoxide in ether (molar ratio of initial reagents, 3: 2: 3) have been performed to synthesize nona(3-methylphenyl)tristiboxane-1,5- diyl-bis(trifluoromethanesulfonate) CF₃OSO₂Sb(3-MeC₆H₄)₃OSb(3-MeC₆H₄)₃OSb(3-MeC₆H₄)₃OSO₂CF₃. PhH (I) separated after recrystallization from a benzene–octane mixture in the form of a benzene solvate and, at an equimolar ratio of initial reagents, hexaphenyldistiboxane-1,3-diyl-bis(3,4-dimethylbenzenesulfonate) separated after recrystallization from toluene in the form of a toluene solvate 3,4-Me₂C₆H₃OSO₂SbPh₃OSbPh₃OSO₂C₆H₃Me₂-3,4. TolH (II). The similar reactions of tris(5-bromo-2- methoxyphenyl)antimony and tris(4-methylphenyl)antimony with 2,5-dimethylbenzenesulfonic and 3,4- dimethylbenzenesulfonic acids, respectively in the presence of tert-butylhydroperoxide (molar ratio, 1: 2: 1) lead to the formation of triarylantimony bis(arenesulfonates) (5-Br,2-MeO,C₆H₃)₃Sb(OSO₂C₆H₃Me₂-2,5)₂ (III) and (4-MeC₆H₄)₃Sb(OSO₂C₆H₃Me₂-3,4)₂ (IV). The Sb atom in the structures of complexes I–IV has a distorted trigonal bipyramidal coordination to the oxygen atoms in axial positions.