Abstraction by Cyanide of Thio Ligand From [Mo^VIOS] and Related Centers: The Crystal and Molecular-Structure of cis-Oxobis[piperidine N-oxido(1-)-O,N]-selenomolybdenum(VI)

Abstract

cis -[ MoOS (C₅H₁₀NO)₂] reacts with cyanide in CDCl₃ solution to produce cis -[MoO₂(C₅H₁₀NO)₂](50-60%) and SCN^- (65-85%). Free C₅H₁₀NH and C₅H₁₀NOH are formed as well, these results suggesting piperidine N- oxido ligand as the source of oxidizing equivalents in the system. Under the same conditions, cis -[MoS₂(C₅H₁₀NO)₂] and cis -[ MoOSe (C₅H₁₀NO)₂] also form cis - [MoO2(C₅H₁₀NO)₂]. The molecular structure of the title compound reveals Mo-Se and Mo-O ( oxo ) bond lengths of 2.299(1) and 1.719(4) Ǻ, and an O-Mo-Se bond angle of 115.3(1)°. The structure is related closely to that of [ MoOS (C₅H₁₀NO)₂], and detailed differences are those expected for substitution of a thio ligand by the larger seleno congener. Crystal data: a 6.977(1), b 21.469(3), c 9.791(2) Ǻ, β 91.50(2)°; P2₁/n; Z 4.