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.

We 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 as PowerPoint slide