Oxidative addition of organic disulfides to low valent N,C,N-chelated organobismuth(I) compound: Isolation, structure and coordination capability of substituted bismuth(III) bis(arylsulfides)

The reaction between in situ prepared THF solution of N,C,N-chelated organobismuth(I) [LBi](n) compound (not isolated), via reaction of LBiCl2 (1) (where L [o,o-C6H3(CH2NMe2)(2)]) with K[B(s-Bu)(3)H] (K-Selectride), and a set of diorganodisulfides ArSSAr gave organobismuth(III) compounds LBi(SAr)(2) 2-7 (where Ar = 2-pyridyl (2), 4-metylthiazol-2-yl (3), thiofen-2-yl (4), 4-tert-butyl-1-iso-propyl-1H-imidazol-2-yl (5), 1-phenyl-1H-tetrazol-5-yl (6), 2-aminophenyl (7)). Compounds 2-7 were characterized by the help of elemental analysis, H-1 and C-13 NMR spectroscopy and in the case of 2, 3 and 6 by the help of single-crystal X-ray diffraction analysis. Compound 7 was unstable in solution and decomposed to compound LBi[S(NH)C6H4] (8), containing five-membered BiSNC2 ring, and the 2-aminothiophenol. Attempts to selectively cleave the Bi-N bond involved in this ring by an acid (such as HCl or acetic acid) failed and led only to the isolation of 1 or acetate LBi(Ac)(2) and elimination of 2-aminothiophenol. Finally, the coordination capability of compound 2 toward both main group (SbCl3, BiCl3, GeCl2 and SnCl2) and transition metal (PdCl2 and PtCl2) compounds was studied. (C) 2013 Elsevier B. V. All rights reserved.