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Diphosphinonitrenium and ‐phosphenium Cations, Jahn‐Teller Distorted Allyl Systems
Author(s) -
Schoeller Wolfgang W.,
Busch Thilo
Publication year - 1990
Publication title -
chemische berichte
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 0009-2940
DOI - 10.1002/cber.19901230506
Subject(s) - chemistry , jahn–teller effect , distortion (music) , allylic rearrangement , symmetry (geometry) , ab initio , planarity testing , symmetry breaking , crystallography , computational chemistry , quantum mechanics , ion , geometry , physics , catalysis , amplifier , biochemistry , organic chemistry , cmos , mathematics , optoelectronics
Ab initio calculations at SCF, MCSCF, and ACPF level were performed on a series of the phosphenium‐ and nitreniumcation family. These show that they possess an allylic π‐system with 4 electrons, which is distorted from planarity when the terminal groups of the allylic system are PR 2 (R H) fragments. The distortion is such as to adopt C 2 symmetry, and is the consequence of Jahn‐Teller distortion via mixing of the energy highest π 2 orbital with an energetically low lying δ * orbital. The latter interaction is only operative if a symmetry breaking from C 2v to C 2 symmetry occurs. The importance of Jahn‐Teller distortion on the biradical character in these systems is investigated by correlation calculations.