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Updated: Sep 23, 2025
Imine Metathesis by Silica-Supported Catalysts Using the Methodology of Surface Organometallic Chemistry
Published on: October 18, 2019
Metathesis between E-C(spn ) and H-C(sp3 ) σ-Bonds (E=Si, Ge; n=2, 3) on an Osmium-Polyhydride
Miguel A Esteruelas1, Ana M López1, Enrique Oñate1
1Departamento de Química Inorgánica, Instituto de Síntesis Química y Catálisis Homogénea (ISQCH), Centro de Innovación en Química Avanzada (ORFEO-CINQA), Universidad de Zaragoza-CSIC, 50009, Zaragoza, Spain.
Abstract:
The silylation of a phosphine of OsH6 (Pi Pr3 )2 is performed via net-metathesis between Si-C(spn ) and H-C(sp3 ) σ-bonds (n=2, 3). Complex OsH6 (Pi Pr3 )2 activates the Si-H bond of Et3 SiH and Ph3 SiH to give OsH5 (SiR3 )(Pi Pr3 )2 , which yield OsH4 {κ1 -P,η2 -SiH-[i Pr2 PCH(Me)CH2 SiR2 H]}(Pi Pr3 ) and R-H (R=Et, Ph), by displacement of a silyl substituent with a methyl group of a phosphine. Such displacement is a first-order process, with activation entropy consistent with a rate determining step occurring via a highly ordered transition state. It displays selectivity, releasing the hydrocarbon resulting from the rupture of the weakest Si-substituent bond, when the silyl ligand bears different substituents. Accordingly, reactions of OsH6 (Pi Pr3 )2 with dimethylphenylsilane, and 1,1,1,3,5,5,5-heptamethyltrisiloxane afford OsH5 (SiR2 R')(Pi Pr3 )2 , which evolve into OsH4 {κ1 -P,η2 -GeH-[i Pr2 PCH(Me)CH2 SiR2 H]}(Pi Pr3 ) (R=Me, OSiMe3 ) and R'-H (R'=Ph, Me). Exchange reaction is extended to Et3 GeH. The latter reacts with OsH6 (Pi Pr3 )2 to give OsH5 (GeEt3 )(Pi Pr3 )2 , which loses ethane to form OsH4 {κ1 -P,η2 -GeH-[i Pr2 PCH(Me)CH2 GeEt2 H]}(Pi Pr3 ).
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