Abstract
A broad set of structural models and theoretical methods has been successfully used for studying both the molecular electron structure of the silacalix[3]phosphinine and the changes of the macrocycle core under the conditions that frequently correspond to its complexes with metals. The macrocycle core of the silacalix[3]phosphinine and its neutral derivatives are strongly deviated from the main molecular plane. The phosphorous electron lone pairs and the π‐cloud of the phosphinine units give the main contribution to the electron valence structure in the silacalix[3]phosphinine and also in its both oxidized and reduced derivatives. Although the electron lone pairs of the P atoms tend to be strongly repulsive, they are either totally or partially extended above all the fragment of the phosphorous atoms depending on geometrical factors or even strongly coupled with the π‐cloud of the phosphinine units. Electronic processes that take away part of the electron density from the macrocyle favor both its planar configuration and the asymmetric distribution of the valence electrons in the silacalix[3]phosphinine and its derivatives. The limit condition to this effect is the appearance of a new in‐plane σ molecular orbital between the P atoms of two neighboring phosphinine units. © 2007 Wiley Periodicals, Inc. J Comput Chem, 2007