A NEW SIMPLE METHOD FOR THE PRODUCTION AND SOME CONVERSIONS OF B[sbnd]S BONDCONTAINING o- AND m-CARBORANYL

Abstract

A new method of synthesis of o- and m-carboranyl-B-thiols and o- and m-carboranyl-B,B'-dithiols via the electrophilic sulfuration of o, m-carboranes with S₂Cl₂ in the presence of AlCl₃ is described. The reaction of o-carborane with excess S₂Cl₂ in the presence of AlCl₃ gives B,B',B″,B″′-tetrathiol-o-carborane. Various chemical conversions of carborane sulfur derivatives are studied. A description is made of carboranyl derivatives of di-, tetra- and hexavalent sulfur, such as sulfenyl chlorides, thiocyanates, disulfides, alkyl- and aryl sulfides, aryl sulfones and aryl sulfoxides. 9-m-Carboranylsulfinic acid was found to readily disproportionate to thiosulfonate and sulfonic acid. The chemical behaviour of o- and m-carboranyl sulfur derivatives in which the sulfur atom is σ-bound to the six-coordinated boron atom was also found to be similar to that of organic sulfur derivatives.