Self‐Reduction of [Ph 4 P][Nb(SCH 2 CH 2 CH 2 S) 3 ] with Formation of a Nb 2 IV Complex

The size of the chelate ring determines the reactivity of Nb v complexes: Whereas [Ph 4 P][Nb(SCH 2 CH 2 S) 3 ] is completely stable in acetonitrile, in the case of the homologous title complex a reductive dimerization takes place. The anion 1 formed initially reacts further with methanol to give 2 , which was isolated as the Ph 4 P‐salt; the structure of this anion is shown on the right.\documentclass{article}\usepackage{amssymb}\pagestyle{empty}\begin{document}$${\begin{array}{ll}&[{\rm Nb_2(SCH_2CH_2CH_2S)_5}]^{2\ominus}\quad{\bf 1}\\&\\&[{\rm Nb_2(OM_e)_3(SCH_2CH_2CH_2S)_3}]^{\ominus}\quad{\bf 2}\end{array}}$$\end{document}