ISSN:
0009-2940
Keywords:
Calculations
;
Jahn-Teller distortion
;
Nitrenium
;
Phosphenium
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
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 PR2 (R — H) fragments. The distortion is such as to adopt C2 symmetry, and is the consequence of Jahn-Teller distortion via mixing of the energy highest π2 orbital with an energetically low lying δ* orbital. The latter interaction is only operative if a symmetry breaking from C2v to C2 symmetry occurs. The importance of Jahn-Teller distortion on the biradical character in these systems is investigated by correlation calculations.
Additional Material:
1 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19901230506
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