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Preparation and Reactivity of a Triphosphenium Bromide Salt: A Convenient and Stable Source of PhosphorusI
Published on: November 22, 2016
Spectroscopic Identification of Diphosphene HPPH and Isomeric Diphosphinyldene PPH2
Bo Lu1, Lina Wang1, Xin Jiang1
1Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, Shanghai, 200433, China.
Abstract:
The simplest diphosphene HPPH and isomeric diphosphinyldene PPH2 features prototype phosphorus-phosphorus multiple bonding properties that have been of long-standing interest in main-group chemistry. Herein, we report the observation of cis-HPPH, trans-HPPH, and PPH2 among the respective laser photolysis products of phosphine (PH3 ) and diphosphine (P2 H4 ) in solid N2 - and Ar-matrices at 10 K. The identification of these P2 H2 isomers with matrix-isolation IR and UV/Vis spectroscopy is supported by D-isotope labeling and the quantum chemical calculations at the CCSD(T)-F12a/cc-pVTZ-F12 level using configuration-selective vibrational configuration interaction theory (VCI). Bonding analyses suggest that the two conformers of HPPH contain standard PP double bonds, whereas, PPH2 resembles P2 in having partial PP triple bond due to the H2 P←P π bonding interaction.
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