Results
Title

The Reactions of Carbon Monoxide with Silyl and Silenyl Lithium – Synthesis and Isolation of the First Stable Tetra‐Silyl Di‐Ketyl Biradical and 1‐Silaallenolate Lithium.

Authors

Kratish, Yosi; Pinchuk, Daniel; Kaushansky, Alexander; Molev, Victoria; Tumanskii, Boris; Bravo‐Zhivotovskii, Dmitry; Apeloig, Yitzhak

Abstract

Reactions of carbon monoxide (CO) with tBu2MeSiLi and (E)‐(tBu2MeSi)(tBuMe2Si)C=Si(SiMetBu2)Li⋅2 THF (4) were studied both experimentally and computationally. Reaction of tBu2MeSiLi with CO in hexane yields the first stable tetra‐silyl di‐ketyl biradical [(tBu2MeSi)2COLi].2 (3). Reaction of 4 with CO yields selectively and quantitatively the first reported 1‐silaallenolate, (tBu2MeSi)(tBuMe2Si)C=C=Si(SiMetBu2)OLi⋅THF (5). Both 3 and 5 were characterized by X‐ray crystallography and biradical 3 also by EPR spectroscopy. Silaallenolate 5 reacts with Me3SiCl to produce siloxy substituted 1‐silaallene (tBu2MeSi)(tBuMe2Si)C=C=Si(SiMetBu2)OSiMe3. The reaction of 4 with CO provides a new route to 1‐silaallenes. The mechanisms of the reactions of tBuMe2SiLi and of 4 with CO were studied by DFT calculations.

Subjects

CARBON monoxide; RARE earth oxides; ELECTRON paramagnetic resonance spectroscopy; X-ray crystallography; SILYL ethers; HEXANE; OXIDATION of carbon monoxide

Publication

Angewandte Chemie, 2019, Vol 131, Issue 52, p19025

ISSN

0044-8249

Publication type

Academic Journal

DOI

10.1002/ange.201910336