A silylene-stabilized ditin(0) complex and its conversion to methylditin cation and distannavinylidene

Shaozhi Du, Fanshu Cao, Xi Chen, Hua Rong, Haibin Song and Zhenbo Mo ()
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Shaozhi Du: Nankai University
Fanshu Cao: Nankai University
Xi Chen: Nankai University
Hua Rong: Nankai University
Haibin Song: Nankai University
Zhenbo Mo: Nankai University

Nature Communications, 2023, vol. 14, issue 1, 1-10

Abstract: Abstract Due to their intrinsic high reactivity, isolation of tin(0) complexes remains challenging. Herein, we report the synthesis of a silylene-stabilized ditin(0) complex (2) by reduction of a silylene-supported dibromostannylene (1) with 1 equivalent of magnesium (I) dimer in toluene. The structure of 2 was established by single crystal X-ray diffraction analysis. Density Functional Theory calculations revealed that complex 2 bears a Sn=Sn double bond and one lone pair of electrons on each of the Sn(0) atoms. Remarkably, complex 2 is readily methylated to give a mixed-valent methylditin cation (4), which undergoes topomerization in solution though a reversible 1,2-Me migration along a Sn=Sn bond. Computational studies showed that the three-coordinate Sn atom in 4 is the dominant electrophilic center, and allows for facile reaction with KHBBus3 furnishing an unprecedented N-heterocyclic silylenes-stabilized distannavinylidene (5). The synthesis of 2, 4 and 5 demonstrates the exceptional ability of N-heterocyclic silylenes to stabilize low valent tin complexes.

Date: 2023
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DOI: 10.1038/s41467-023-42953-5

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