Journal of Physical Chemistry A, Vol.120, No.21, 4211-4222, 2016
Conciliatory Inductive Model Explaining the Origin of Changes in the eta(2)-SiH Bond Length Caused by Presence of Strongly Electronegative Atoms X (X = F, CI) in Cp(OC)(2)Mn[eta(2)-H(SiH3-nXn)] (n=0-3) Complexes
complexes a new model, called the Conciliatory Inductive Model, is being proposed.Using three theoretical methods, QTAIM, IQA, and NCI, we analyze an influence of halogen atoms X (X = F, Cl) substituted at various positions in the -SiH3-nXn group on the charge density distribution within the eta(2)-SiH bond and on the SiH bond energies in Cp(OC)(2)Mn[eta(2)-H(SiH3-nXn)] complexes and isolated HSiH3-nXn molecules. It is shown that shortening of the eta(2)-SiH bond in Cp(OC)(2)Mn[eta(2)-H(SiH3-nXn)] complexes should be considered as a normal inductive result of halogenation. This eta(2)-SiH bond's compression may, however, be overcome by a predominant elongation resulting from a contingent presence of a halogen atom at position trans to the eta(2)-SiH bond. This traps effect is particularly large for bulky and highly polarizable chlorine. Moreover, peculiar properties of the trans chlorine atom are manifested in several ways. To explain the origin of all the observed changes in both the length and the electron charge distribution of the eta(2)-SiH bond in investigated Cp (OC)(2)Mn[eta(2)-H(SiH3-nXn)]