Formation and Reactivity of heavy Group 14-15 bonds

Abstract

A series of low-valent Group 14-15 compounds were obtained starting from [(Dipp₂ NacNac)MCl] (M=Ge-Pb) (I-III) (Dipp₂ NacNac=HC{C(Me)N(Dipp)}₂ ) and M'E(SiMe₃ )₂ (M'=Li, E=As; M'=K, E=Sb, Bi) (IV-VI). In the course of this investigations we were able to fully characterize all permutations except Pb-Bi for compounds of the composition [(Dipp₂ NacNac)ME(SiMe₃ )₂ ] (1_E : M=Ge, 2_E : M=Sn, 3_E : M=Pb). Thus, we report the first low valent tetrelene with Sn-Bi bond. All isolated compounds, were examined by NMR spectroscopy, IR spectroscopy and except compound 1_As by X-ray structure analysis. Moreover, were examined UV-Vis spectroscopy and investigated the reactivity of these compounds towards different substrates in more detail. Starting with the compound [(Dipp₂ NacNac)SnAs(SiMe₃ )₂ ] (2_As ), the reaction with red selenium yields [(Dipp₂ NacNac)Sn-Se-As(SiMe₃ )₂ ] (4) which exhibits a Sn-Se-As chain.

Keywords: antimony; bismuth; lead; low-valent compounds; tin.