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Updated: Dec 3, 2025

Imine Metathesis by Silica-Supported Catalysts Using the Methodology of Surface Organometallic Chemistry
Published on: October 18, 2019
An Iminophosphonamido-Chlorosilylene as a Strong σ-Donating NHSi Ligand: Synthesis and Coordination Chemistry
Shintaro Takahashi1, Jueri Sekiguchi1, Akihiko Ishii1
1Department of Chemistry, Graduate School of Science and Engineering, Saitama University, Shimo-okubo, Sakura-ku, Saitama, 338-8570, Japan.
Abstract:
The N-heterocyclic silylene (NHSi) [Ph2 P(t BuN)2 ]SiCl (1), supported by an iminophosphonamide ligand, was obtained from the dehydrochlorination of [Ph2 P(t BuN)2 ]SiHCl2 (2) with LiN(SiMe3 )2 . NHSi 1 contains an extremely high-energy HOMO level and consequently displays unique coordination behavior toward RhI complexes. When 1 was treated with 1/4 of an equivalent of [RhCl(cod)]2 (cod=1,5-cyclooctadiene), the 14-electron Y-shaped bis(chlorosilylene) RhI complex 5 was obtained as dark purple crystals. The reaction of 1 with 1/6 of an equivalent of [RhCl(cod)]2 yielded the cationic tris(silylene)-RhI complex [6]+ ⋅Cl- as red crystals, wherein a two-coordinated silylene ligand engages in a Si=Rh double bond. A structural analysis of 5 and [6]+ ⋅Cl- revealed that the central rhodium atoms adopt trigonal and square-planar coordination geometries, respectively, with considerably shortened Si-Rh bonds [5: 2.1605(5) Å; [6]+ : 2.133(1) Å].
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