Synthesis and Structure of a Base‐Stabilized C‐Phosphino‐Si‐Amino Silyne

Abstract

A silyne seeker: The synthesis of the first isolable silyne, which is stabilized by a phosphine ligand, has been achieved (see picture). An X‐ray diffraction study reveals a very short silicon–carbon bond, as predicted computationally for SiC bonds. This species has a certain degree of carbenic character, and this result shows that the phosphonium sila‐ylide fragment acts as a strong π‐donating and π‐accepting substituent.

Synthesis of a Stable Disilyne Bisphosphine Adduct and Its Non‐Metal‐Mediated CO2 Reduction to CO

“…A similar ligand effect was observed in the recently synthesized phosphine-stabilized silyne showing a short Si À C bond corresponding to a triple bond, despite the coordination of phosphine ligand. [13] Although this new species 2 is stable at room temperature under inert atmosphere for weeks, it shows a high reactivity with carbon dioxide. Indeed, the reaction of 2 with CO 2 is complete upon mixing to afford the aminosilicate 5 with two pentacoordinate silicon atoms (78 % yield of isolated product, Scheme 3).…”

Synthesis and Thermal Decomposition of Heavy Tetrylenes Bearing N‐Aminocarbazolyl Substituents

“…[13,14] Am uch less developed field of chemistry focuseso nt he relatedh eteronuclear multiple bonds. Therea re reports on many instanceso fs ilenes, [15] phosphaalkenes, [16] and phosphaalkines, [17] since the seminal reports by the groupsofBrook and Becker.Other heteroatomic multiple bond systems were prepared more recently,s uch as analogueso fd iazonium salts ([R-NE] + ,E= P, As), [18,19] as well as exampleso fasilyne( R-SiC-R') [20] and ag ermyne (R-GeC-…”

Reversible Insertion of Unactivated Alkenes into Silicon(II)–Tin Bonds

“…Herein, we report that alkene insertion into the Si II ÀSn bond of trimethylstannylsubstituted silylene-phosphine complexes 1-Sn takes place without any catalyst and under very mild conditions. Of particular interest is the reversibility of the insertion reaction even at room temperature.The trimethylstannyl-substituted silylene complexes 1-Sn can be prepared readily from the corresponding chlorosilylene [18] derivatives by treatment with one equivalent of trimethylstannyllithium. Products 1 a-Sn (81 % yield) and 1 b-Sn (85 % yield) could both be isolated in the solid state and were characterized in solution as well as by X-ray diffraction analysis (Figure 1, top).…”

“…The trimethylstannyl-substituted silylene complexes 1-Sn can be prepared readily from the corresponding chlorosilylene [18] derivatives by treatment with one equivalent of trimethylstannyllithium. Products 1 a-Sn (81 % yield) and 1 b-Sn (85 % yield) could both be isolated in the solid state and were characterized in solution as well as by X-ray diffraction analysis (Figure 1, top).…”