Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
 
The Origin of Relative Stability of Di-µ-oxo M–M Chiral Salen Complexes [M–M = Ti(IV)–Ti(IV), V(IV)–V(IV), Cr(IV)–Cr(IV), and Mn(IV)–Mn(IV)]: A Quantum-Chemical Analysis
Radhika NarayananArchana VellothTakuya KurahashiHiroshi FujiiMasahiko Hada
Author information
JOURNALS RESTRICTED ACCESS

Volume 89 (2016) Issue 4 Pages 447-454

Details
View on the journal site Contact us
Abstract

Di-µ-oxo dimetal cores can form dinuclear complexes with definite stereochemistries. Recent studies describing the synthesis and evaluation of titanium(IV) and manganese(IV) di-µ-oxo dimetal chiral salen complexes prompted us to explore the corresponding vanadium(IV) and chromium(IV) complexes. We therefore modeled a series of di-µ-oxo dimetal complexes of titanium(IV), vanadium(IV), chromium(IV), and manganese(IV) with tetradentate salen ligands bearing different degrees of steric bulk. Quantum mechanical calculations were conducted to compare the stabilities and molecular structures of these complexes. The results of natural population analysis gave an insight into the charge distribution characteristics of the di-µ-oxo dimetal cores of these complexes. Our calculations showed that the di-µ-oxo dimetal complexes bearing the least sterically encumbered model ligand 1 preferred the M-helical form over the P-helical one. In the titanium(IV) and chromium(IV) complexes containing a practical chiral salen ligand 2, the P-helical form was found to be more stable than the corresponding M-form. In contrast, the corresponding vanadium(IV) and manganese(IV) complexes preferred to exist in the M-helical form. The degree of distortion of the di-µ-oxo dimetal core and the inter ligand interactions were key factors for determining the stability of these complexes.

Information related to the author
© 2016 The Chemical Society of Japan
Previous article Next article

Recently visited articles
feedback
Top