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An Isolable Tetrasilicon Analogue of a Planar Bicyclo[1.1.0]butane with π-Type Single-Bonding Character

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2020)

期刊

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY

卷 142, 期 22, 页码 9920-9924

出版社

AMER CHEMICAL SOC

DOI: 10.1021/jacs.0c03874

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Chemistry, Multidisciplinary

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JSPS KAKENHI [JP25248010, JP17H03015]

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Isolable compounds that contain pi bonding without an underlying sigma-bond framework (pi-type single bonding) remain scarce. Herein we report the synthesis and properties of 1,3-diiodotetrasilabicyclo[1.1.0]butane 2 via 1,2-diiodination of the corresponding bridgehead disilene 1. Single-crystal X-ray diffraction analysis of 2 revealed a planar bicyclic silicon ring with a planar geometry around the bridgehead silicon atoms and a long bridgehead Si-Si distance. DFT calculations suggested a pi-type single bond between the bridgehead Si atoms in 2 and indicated that the high planarity of 2 should most likely be attributed to the bulky substituents at the bridge positions.

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