Synthesis and reactions of some new heterocyclic bismuth-(III) and -(V) compounds. 5,10-Dihydrodibenzo[b,e]bismine and related systems

New heterocyclic bismuth(III) compounds, 5-(4′-methylphenyl)-5,10-dihydrodibenzo[b,e]bismine 4, its 10-oxa and 10-thia analogues 5, 6 and 7 were synthesized and their reactions with benzoyl chloride and sulfuryl dichloride were investigated. Stable 10-alkynyl, alkenyl and alkyl-5-thiabismuth(III) compounds 13–15 and 19–21 were obtained from 10-halogeno derivatives 8 and 17, but not from 3 and 16. X-Ray structure analysis of compound 13 suggests a possible role for transannular interaction between the bismuth and heteroatom functions at the 5-position for the stabilization of labile chlorine–bismuth and aliphatic carbon–bismuth bonds in those systems.