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Isolation and Characterization of Radical Anions Derived from a Boryl‐Substituted Diphosphene
Author(s) -
Asami Shunsuke,
Ishida Shintaro,
Iwamoto Takeaki,
Suzuki Katsunori,
Yamashita Makoto
Publication year - 2017
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201611762
Subject(s) - chemistry , electron paramagnetic resonance , hyperfine structure , crystallography , radical , atomic orbital , absorption spectroscopy , molecular orbital , photochemistry , spectroscopy , electron , molecule , nuclear magnetic resonance , atomic physics , organic chemistry , physics , quantum mechanics
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.