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On the Electronic Structure of Phosphabutatriene and Related Phosphacumulenes. A Theoretical Study
Author(s) -
Schoeller Wolfgang W.,
Welz Udo,
Haug Wilfried,
Busch Thilo
Publication year - 1991
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.19911240205
Subject(s) - chemistry , atomic orbital , cyclobutane , substituent , molecular orbital , crystallography , computational chemistry , electronic structure , stereochemistry , molecule , ring (chemistry) , quantum mechanics , organic chemistry , physics , electron
The title compound phosphabutatriene possesses two energetically closely spaced frontier orbitals, as in methylenephosphane and in phosphaallene. They are built up from the π system or the s̀ orbital of phosphorus by interaction with neighboring π bonds. The extension of these frontier orbitals over all (heavy) atoms makes self‐dimerization to different cyclobutane derivatives feasible. Substituent effects on the ordering of s̀ and π are analyzed. Vibrational analyses indicate PC vibrations of low intensity which decrease with increasing length of the heterocumulene chain. The analysis is extended to the two next higher homologs, which are hitherto experimentally unknown.