Synthesis and structure of N,C-chelated organoantimony(v) and organobismuth(v) compounds

The reaction of N,C-intramolecularly coordinated organoantimony(iii) and organobismuth(iii) compounds LMCl2 (M = Sb () or Bi () and L = [o-(CH[double bond, length as m-dash]N-2,6-iPr2C6H3)C6H4]) with phenyllithium in a 1 : 1 or 1 : 2 molar ratio gave compounds LM(Ph)Cl (M = Sb () or Bi ()) and LMPh2 (M = Sb () or Bi ()) in moderate to good yields. Compound could also be prepared by the treatment of the lithium compound LLi with in situ prepared PhSbCl2. Oxidation of the antimony(iii) compounds , and with one equivalent of SO2Cl2 proceeded smoothly with formation of organoantimony(v) compounds LSbCl4 (), LSb(Ph)Cl3 () and LSbPh2Cl2 () in nearly quantitative yields. Compounds are yellowish solids that are stable for a long time even in the presence of air. In contrast, only organobismuth(iii) compounds and could be successfully oxidized using SO2Cl2 to give compounds LBi(Ph)Cl3 () and LBiPh2Cl2 (). Compound is stable, but compound readily decomposed in solution and could not be isolated and stored for a longer period. All attempts to prepare compound LBiCl4 by the oxidation of with SO2Cl2 failed and resulted only in a mixture of products. All studied compounds were characterized by electrospray ionization (ESI) mass spectrometry, and (1)H and (13)C NMR spectroscopy. The molecular structures of , and were unambiguously established using single-crystal X-ray diffraction analysis.