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A Boryl‐Substituted Diphosphene: Synthesis, Structure, and Reaction with n ‐Butyllithium To Form a Stabilized Adduct by pπ‐pπ Interaction
Author(s) -
Asami Shunsuke,
Okamoto Masafumi,
Suzuki Katsunori,
Yamashita Makoto
Publication year - 2016
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201607995
Subject(s) - chemistry , adduct , substituent , borylation , reagent , nucleophile , medicinal chemistry , crystal structure , crystallography , organic chemistry , catalysis , aryl , alkyl
A boryl‐substituted diphosphene was synthesized through the nucleophilic borylation of PCl 3 with a borylzinc reagent, followed by a reduction with Mg. A combined analysis of the resulting diboryldiphosphene by single‐crystal X‐ray diffraction, DFT calculations, and UV/Vis spectroscopy revealed a σ‐electron‐donating effect for the boryl substituent that was slightly weaker than that of the 2,4,6‐tri‐ tert ‐butylphenyl (Mes*) ligand. The reaction of this diboryldiphosphene with n BuLi afforded a boryl‐substituted phosphinophosphide that was, in comparison with the thermally unstable Mes*‐substituted diaryldiphosphene, stabilized by a π‐electron‐accepting effect of the boryl substituent.