title: A Boryl-Substituted Diphosphene: Synthesis, Structure, and Reaction with n-Butyllithium To Form a Stabilized Adduct by pπ-pπ Interaction.
abstract: A boryl-substituted diphosphene was synthesized through the nucleophilic borylation of PCl3 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.
authors.affiliation: Department of Applied Chemistry, Faculty of Science and Engineering, Chuo University, 1-13-27 Kasuga, Bunkyo-ku, Tokyo, 112-8551, Japan.
authors.forename: Shun-Suke
authors.initials: SS
authors.lastname: Asami
authors.affiliation: Department of Applied Chemistry, Faculty of Science and Engineering, Chuo University, 1-13-27 Kasuga, Bunkyo-ku, Tokyo, 112-8551, Japan.
authors.forename: Masafumi
authors.initials: M
authors.lastname: Okamoto
authors.affiliation: Department of Applied Chemistry, Faculty of Science and Engineering, Chuo University, 1-13-27 Kasuga, Bunkyo-ku, Tokyo, 112-8551, Japan.
authors.forename: Katsunori
authors.initials: K
authors.lastname: Suzuki
authors.affiliation: Department of Applied Chemistry, Faculty of Science and Engineering, Chuo University, 1-13-27 Kasuga, Bunkyo-ku, Tokyo, 112-8551, Japan. makoto@oec.chem.chuo-u.ac.jp.
authors.forename: Makoto
authors.identifier: 0000-0002-3665-5311
authors.initials: M
authors.lastname: Yamashita
keywords: boron; boryllithium; diphosphenes; main group chemistry; substituent effects