Isolation and Characterization of Radical Anions Derived from a Boryl-Substituted Diphosphene

Shun Suke Asami; Shintaro Ishida; Takeaki Iwamoto; Katsunori Suzuki; Makoto Yamashita

doi:10.1002/anie.201611762

Isolation and Characterization of Radical Anions Derived from a Boryl-Substituted Diphosphene

Shun Suke Asami, Shintaro Ishida, Takeaki Iwamoto, Katsunori Suzuki, Makoto Yamashita

SCI - Chemistry

Research output: Contribution to journal › Article › peer-review

29 Citations (Scopus)

Abstract

Radical anions of a diphosphene with two boryl substituents were isolated and characterized by single-crystal X-ray diffraction, electron spin resonance (ESR), and UV/Vis absorption spectroscopy as well as DFT calculations. Structural analysis of the radical anions revealed an elongation of the P=P bond and a contraction of the B−P bonds relative to the neutral diphosphene. The UV/Vis spectra of these radical anions showed a strong absorption in the visible region, which was assigned to SOMO-related transitions on the basis of DFT calculations. The ESR spectra revealed that the hyperfine coupling constant with the phosphorus nuclei is the smallest that has been reported thus far. The results of the DFT calculations furthermore suggest that this should be attributed to a soaking of electron spin to the vacant p orbitals of the boryl substituents.

Original language	English
Pages (from-to)	1658-1662
Number of pages	5
Journal	Angewandte Chemie - International Edition
Volume	56
Issue number	6
DOIs	https://doi.org/10.1002/anie.201611762
Publication status	Published - 2017 Feb

Keywords

ESR spectroscopy
boron
density functional calculations
diphosphenes
radical anions

ASJC Scopus subject areas

Catalysis
Chemistry(all)

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title = "Isolation and Characterization of Radical Anions Derived from a Boryl-Substituted Diphosphene",

abstract = "Radical anions of a diphosphene with two boryl substituents were isolated and characterized by single-crystal X-ray diffraction, electron spin resonance (ESR), and UV/Vis absorption spectroscopy as well as DFT calculations. Structural analysis of the radical anions revealed an elongation of the P=P bond and a contraction of the B−P bonds relative to the neutral diphosphene. The UV/Vis spectra of these radical anions showed a strong absorption in the visible region, which was assigned to SOMO-related transitions on the basis of DFT calculations. The ESR spectra revealed that the hyperfine coupling constant with the phosphorus nuclei is the smallest that has been reported thus far. The results of the DFT calculations furthermore suggest that this should be attributed to a soaking of electron spin to the vacant p orbitals of the boryl substituents.",

keywords = "ESR spectroscopy, boron, density functional calculations, diphosphenes, radical anions",

author = "Asami, {Shun Suke} and Shintaro Ishida and Takeaki Iwamoto and Katsunori Suzuki and Makoto Yamashita",

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AU - Asami, Shun Suke

AU - Ishida, Shintaro

AU - Iwamoto, Takeaki

AU - Suzuki, Katsunori

AU - Yamashita, Makoto

PY - 2017/2

Y1 - 2017/2

N2 - Radical anions of a diphosphene with two boryl substituents were isolated and characterized by single-crystal X-ray diffraction, electron spin resonance (ESR), and UV/Vis absorption spectroscopy as well as DFT calculations. Structural analysis of the radical anions revealed an elongation of the P=P bond and a contraction of the B−P bonds relative to the neutral diphosphene. The UV/Vis spectra of these radical anions showed a strong absorption in the visible region, which was assigned to SOMO-related transitions on the basis of DFT calculations. The ESR spectra revealed that the hyperfine coupling constant with the phosphorus nuclei is the smallest that has been reported thus far. The results of the DFT calculations furthermore suggest that this should be attributed to a soaking of electron spin to the vacant p orbitals of the boryl substituents.

AB - Radical anions of a diphosphene with two boryl substituents were isolated and characterized by single-crystal X-ray diffraction, electron spin resonance (ESR), and UV/Vis absorption spectroscopy as well as DFT calculations. Structural analysis of the radical anions revealed an elongation of the P=P bond and a contraction of the B−P bonds relative to the neutral diphosphene. The UV/Vis spectra of these radical anions showed a strong absorption in the visible region, which was assigned to SOMO-related transitions on the basis of DFT calculations. The ESR spectra revealed that the hyperfine coupling constant with the phosphorus nuclei is the smallest that has been reported thus far. The results of the DFT calculations furthermore suggest that this should be attributed to a soaking of electron spin to the vacant p orbitals of the boryl substituents.

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KW - density functional calculations

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KW - radical anions

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