Premium
The Role of Bulkiness in Haptotropic Shifts of Metal–Cumulene Complexes
Author(s) -
HuidobroMeezs Isaac L.,
SegoviaPoncelis Midori,
BarqueraLozada José Enrique
Publication year - 2016
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201600635
Subject(s) - cumulene , chemistry , steric effects , carbyne , metal , molecule , computational chemistry , stereochemistry , photochemistry , crystallography , organic chemistry , carbene , catalysis
In metal–cumulene complexes, the metal easily slides through the double bonds of the chain. A series of late‐transition‐metal–[5]cumulene complexes has been studied by theoretical and experimental methods in order to understand the factors that control such haptotropic shifts. The bulkiness of the cumulene terminal groups plays a central role in the tautomeric preferences. The quantum theory of atoms in molecules and the electron localizability indicator show that the M–C bond closer to the terminal groups is significantly weakened by steric interactions between these groups and the rest of ligands around the metal center. The results emphasize that special attention should be paid to the orientation of both the bulky substituents at the cumulene and other voluminous ligands around the metal, because the orientation of such moieties is important in predicting the direction of the haptotropic equilibrium correctly.