Formation and Reactivity of Organo‐Functionalized Tin Selenide Clusters

Reactions of R¹SnCl₃ (R¹=CMe₂CH₂C(O)Me) with (SiMe₃)₂Se yield a series of organo‐functionalized tin selenide clusters, [(SnR¹)₂SeCl₄] ( 1 ), [(SnR¹)₂Se₂Cl₂] ( 2 ), [(SnR¹)₃Se₄Cl] ( 3 ), and [(SnR¹)₄Se₆] ( 4 ), depending on the solvent and ratio of the reactants used. NMR experiments clearly suggest a stepwise formation of 1 through 4 by subsequent condensation steps with the concomitant release of Me₃SiCl. Furthermore, addition of hydrazines to the keto‐functionalized clusters leads to the formation of hydrazone derivatives, [(Sn₂(μ‐R³)(μ‐Se)Cl₄] ( 5 , R³=[CMe₂CH₂CMe(NH)]₂), [(SnR²)₃Se₄Cl] ( 6 , R²=CMe₂CH₂C(NNH₂)Me), [(SnR⁴)₃Se₄][SnCl₃] ( 7 , R⁴=CMe₂CH₂C(NNHPh)Me), [(SnR²)₄Se₆] ( 8 ), and [(SnR⁴)₄Se₆] ( 9 ). Upon treatment of 4 with [Cu(PPh₃)₃Cl] and excess (SiMe₃)₂Se, the cluster fragments to form [(R¹Sn)₂Se₂(CuPPh₃)₂Se₂] ( 10 ), the first discrete Sn/Se/Cu cluster compound reported in the literature. The derivatization reactions indicate fundamental differences between organotin sulfide and organotin selenide chemistry.