Nature of transannular intramolecular interactions in group 4 and 6 metallatranes: a combined density functional theory and atoms in molecules theory study.
Density functional calculations coupled with quantum theory of atoms in molecules analysis were carried out on Group 4 and 6 metallatranes with special emphasis on the nature of transannular M···N bonds present in these molecules. Substituents at both the apical and equatorial positions are found to influence the extent of transannular interaction. The degree of pyramidalization around the metal and the bridgehead nitrogen atom play a key role in strengthening or weakening the M···N bond. The stability of these molecules are found to depend to a large extent on the strength of M···N bonds with significant contribution coming in from metal-equatorial and metal-apical bonds. Group 6 metallatranes are found to have stronger transannular bonds and, hence, higher stabilization energies than their Group 4 counterparts. Atoms in molecules theory analysis reveals the presence of a considerable amount of covalent character in the M···N bonds which increase from Group 4 to Group 6.
Phukan
Ashwini K
AK
Department of Chemical Sciences, Tezpur University, Napaam 784028, Assam, India. ashwini@tezu.ernet.in
Guha
Ankur Kanti
AK
D008968:Molecular Conformation; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D011789:Quantum Theory; D028561:Transition Elements / Q000737:chemistry*
D009942:Organometallic Compounds; D028561:Transition Elements