Pyridine‐Stabilized Cationic Silanethione Tungsten Complexes: Synthesis, Structures, and Reactivity

Abstract

AbstractSilanethione compounds, R2Si=S, have been recognized as highly reactive species. One reliable way to stabilize silanethione is its coordination to transition metal fragments to convert silanethione‐coordinated transition metal complexes. Herein, we report the synthesis, structure, and reactivity of a second cationic silanethione tungsten complex [Cp*(OC)3W{S=SiR2(py)}]TFPB (R=Me (5 a), Ph (5 b), Cp*: η5‐C5Me5, py: pyridine, and TFPB−: [B{3,5‐(CF3)2C6H3}4]−). Complex 5 was obtained by H− abstraction from the Si atom in the corresponding silylsulfanyl complex Cp*(OC)3W(SSiR2H) (4) with Ph3CTFPB, followed by the addition of pyridine. The reaction of 5 with PhNCS and PMe3 produced [Cp*(OC)3W{SSiR2N(Ph)C(PMe3)2}]TFPB (R=Me (6 a), Ph (6 b)) via the elimination of pyridine and the addition of the 1,3‐dipolar species PhNC(PMe3)2 (A) to the Si atom.