Oxidative Addition of Diphenyldichalcogenides PhEEPh (E = S, Se, Te) to Low-Valent CN- and NCN-Chelated Organoantimony and Organobismuth Compounds

Abstract

The reactions of the organoantimony(I) compound L14Sb4 (1) (where L1 = [o-C6H4(CH═NC6H3(i-Pr)2-2,6)]) with diphenyldichalcogenides PhEEPh (E = S, Se, or Te) gave compounds L1Sb(EPh)2 (E = S (2), Se (3), Te (4)) as the result of the oxidative addition of the antimony(I) atom across the chalcogen–chalcogen bond. The reaction of diphenyldichalcogenides PhEEPh with an in situ prepared organobismuth(I) compound (via reaction of the parent chloride L1BiCl2 (5) with two equivalents of K[B(s-Bu)3H]) gave surprisingly diorganobismuth compounds L12Bi(EPh) (E = S (6), Se (7), Te (8)) as the major products along with only a trace amount of the intended compounds L1Bi(EPh)2 (E = S (9), Se (10), Te (11)). It turned out that this is the result of instability of 9–11 in solution, and their decomposition provided compounds 6–8. The bismuth compounds containing the pincer-type ligand L2 (L2 = [o,o-C6H3(CH2NMe2)2]) containing an extra donor pendant arm were studied with the aim to support their stability by an additional N→...