Volume 126, Issue 36 pp. 9723-9725

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Syntheses, Structures, and Reactivities of Two Chalcogen-Stabilized Carbones^†

Tomohito Morosaki,

Tomohito Morosaki

Department of Applied Molecular Chemistry, College of Industrial Technology, Nihon University, Chiba 275-8575 (Japan)

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Tsubasa Suzuki,

Tsubasa Suzuki

Department of Applied Molecular Chemistry, College of Industrial Technology, Nihon University, Chiba 275-8575 (Japan)

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Dr. Wei-Wei Wang,

Dr. Wei-Wei Wang

Fukui Institute for Fundamental Chemistry, Kyoto University, Kyoto 606-8103 (Japan)

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Prof. Shigeru Nagase,

Prof. Shigeru Nagase

Fukui Institute for Fundamental Chemistry, Kyoto University, Kyoto 606-8103 (Japan)

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Prof. Takayoshi Fujii,

Corresponding Author

Prof. Takayoshi Fujii

[email protected]

Department of Applied Molecular Chemistry, College of Industrial Technology, Nihon University, Chiba 275-8575 (Japan)

Department of Applied Molecular Chemistry, College of Industrial Technology, Nihon University, Chiba 275-8575 (Japan)Search for more papers by this author

Tomohito Morosaki,

Tomohito Morosaki

Department of Applied Molecular Chemistry, College of Industrial Technology, Nihon University, Chiba 275-8575 (Japan)

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Tsubasa Suzuki,

Tsubasa Suzuki

Department of Applied Molecular Chemistry, College of Industrial Technology, Nihon University, Chiba 275-8575 (Japan)

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Dr. Wei-Wei Wang,

Dr. Wei-Wei Wang

Fukui Institute for Fundamental Chemistry, Kyoto University, Kyoto 606-8103 (Japan)

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Prof. Shigeru Nagase,

Prof. Shigeru Nagase

Fukui Institute for Fundamental Chemistry, Kyoto University, Kyoto 606-8103 (Japan)

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Prof. Takayoshi Fujii,

Corresponding Author

Prof. Takayoshi Fujii

[email protected]

Department of Applied Molecular Chemistry, College of Industrial Technology, Nihon University, Chiba 275-8575 (Japan)

Department of Applied Molecular Chemistry, College of Industrial Technology, Nihon University, Chiba 275-8575 (Japan)Search for more papers by this author

First published: 07 July 2014

https://doi.org/10.1002/ange.201404795

Citations: 15

^†

This work was partially supported by a special grant from the College of Industrial Technology, Nihon University. We thank Dr. T. Nakahodo (Kinki University) for the crystallographic analysis of 7.

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Abstract

Electronic effects on the central carbon atom of carbone, generated by the replacement of the S^IV ligand of carbodisulfane (CDS) with other chalcogen ligands (Ph₂E, E=S or Se), were investigated. The carbones Ph₂E→C←SPh₂(NMe) [E=S(1) or Se(2)] were synthesized from the corresponding salts, and their molecular structures and electronic properties were characterized. The carbone 2 is the first carbone containing selenium as the coordinated atom. DFT calculations revealed the electronic structures of 1 and 2, which have two lone pairs of electrons at the carbon center. The trend in HOMO energy levels, estimated by cyclic voltammetry measurements, for the carbones and CDS follows the order of 2>1>CDS. Analysis of a doubly protonated dication and trication complex revealed that the central carbon atom of 2 behaves as a four-electron donor.

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Syntheses, Structures, and Reactivities of Two Chalcogen-Stabilized Carbones^†