Herein, cobalt(I) complexes with a monodentate N-heterocyclic imino substituted silylene were synthesized and characterized. The cobalt(I) hydride complex 3 exhibits high catalytic efficiency in the hydrogenation of olefins with goo...
Artikel
Pyridine‐Stabilized Cationic Silanethione Tungsten Complexes: Synthesis, Structures, and Reactivity
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The pyridine-stabilized cationic silanethione tungsten complexes [Cp*(OC)3W{S=SiR2(py)}]TFPB (R=Me, Ph) were prepared by H− abstraction from the corresponding silylsulfanyl complexes. The reactions with PhNCS and PMe3 afforded addition products of the PhNC(PMe3)2 to the silicon atoms of the S=SiR2 fragments.
Abstract
Silanethione 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.
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