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 oxidative addition of disulfides to bismuth(I) compound led to bismuth(III) bis(arylsulfides).•Their structure was determined both in the solid state and in solution.•Their coordination capability toward metal chlorides was studied.

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)3H] (K-Selectride), and a set of diorganodisulfides ArSSAr gave organobismuth(III) compounds LBi(SAr)22–7 (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, 1H and 13C 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.

Graphical abstractWe have demonstrated that in situ prepared N,C,N-chelated organobismuth(I) compound is good precursor for preparation of a variety of organobismuth(III) bis(arylsulfides) via oxidative addition of organic disulfides to low valent bismuth(I) center.Figure optionsDownload full-size imageDownload as PowerPoint slide