Strained and Reactive Donor/Acceptor‐Supported Metallasilanone

We report on reactions of heteroleptic metallasilylenes CO 2 , N 2 O, and Me 3 SiN 3 , yielding the corresponding carbonate complexes L 1 (Cl)MOSi(CO 3 -k 2 O,OÀ )L 2 (M = Al 3, Ga 4), silanoic esters L 1 (Cl)MOSi(O)L 2 (M = Al 5, Ga 6), and silaimine L 1 (Cl)GaSi(NSiMe 3 )L 2 (8), whereas {L 2 Si[N(SiMe 3 )Al(Cl)C-C(Me)NDipp][CHC(Me)N(Dipp)]} 7 was formed by CÀ C bond cleavage of the L 1 ligand. Compounds 3-8 were characterized by NMR ( 1 H, 13 C) and IR spectroscopy, elemental analysis and single crystal X-ray diffraction.

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Small‐Molecule Activation by Heteroleptic Metallasilylenes

Schoening

Wölper

Schulz

2022

Eur J Inorg Chem

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

et al. 2023

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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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Strained and Reactive Donor/Acceptor‐Supported Metallasilanone

Cited by 2 publications

References 91 publications

Small‐Molecule Activation by Heteroleptic Metallasilylenes

Small‐Molecule Activation by Heteroleptic Metallasilylenes

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

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