Synthesis of phosphinochalcogenoic amidato complexes of divalent transition metals and their thermolysis to metal selenide and telluride phases 

Abstract

Protolysis of the transition-metal diamides [M{N(SiMe₃)₂}₂(thf ) _n] (M = Cr, Mn, Fe or Co) with 2 equivalents of phosphinochalcogenoic amides Bu^t₂P(E)NHR (E = Se or Te, R = Prⁱ or cyclo-C₆H₁₁) gave a series of thermally stable metal–selenium and –tellurium complexes [M{Bu^t₂P(E)NR}₂]. The complex [Ni{Bu^t₂P(Se)NR}₂] was obtained from Li[Bu^t₂(Se)NR] and [NiCl₂(PMe₃)₂]. The compounds sublime readily under reduced pressure and are suitable for the gas-phase deposition of metal chalcogenide films. The selenium precursors lead to MSe (M = Cr, Mn, Fe or Ni), while tellurium complexes afford MTe₂ (M = Fe, Mn or Co). By contrast, [Co{Bu^t₂P(Se)NR}₂] gives Co₃Se₄, while [Ni{Bu^t₂P(Se)NR}₂] generates NiSe or Ni₆Se₅, depending on the deposition conditions.

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