title: Joint spectroscopic and theoretical investigations of transition metal complexes involving non-innocent ligands.
abstract: A series of transition metal complexes involving non-innocent o-dithiolene and o-phenylenediamine ligands has been characterized in detail by various spectroscopic methods like magnetic circular dichroism (MCD), absorption (abs), resonance Raman (rR), electron paramagnetic resonance (EPR), and sulfur K-edge X-ray absorption spectroscopies. A computational model for the electronic structure of the complexes is then proposed based on the density functional theory (DFT) or ab-initio methods, which can successfully account for the observed trends in the experimental spectra (MCD, rR, and abs) of the complexes. Based on these studies, the innocent vs non-innocent nature of the ligands in a given transition metal complex is found to be dependent on the position of the central metal ion in the periodic table, its effective nuclear charge in interplay with relativistic effects.
authors.affiliation: Institut für Physikalische und Theoretische Chemie, Universität Bonn, Wegelerstrasse 12, D-53115 Bonn, Germany.
authors.forename: Kallol
authors.initials: K
authors.lastname: Ray
authors.forename: Taras
authors.initials: T
authors.lastname: Petrenko
authors.forename: Karl
authors.initials: K
authors.lastname: Wieghardt
authors.forename: Frank
authors.initials: F
authors.lastname: Neese
mesh_terms: D002942:Circular Dichroism; D018360:Crystallography, X-Ray; D004578:Electron Spin Resonance Spectroscopy; D007477:Ions; D008024:Ligands; D008280:Magnetics; D008956:Models, Chemical; D008958:Models, Molecular; D008962:Models, Theoretical; D008968:Molecular Conformation; D012984:Software; D013057:Spectrum Analysis / Q000379:methods*; D013059:Spectrum Analysis, Raman; D013696:Temperature; D028561:Transition Elements / Q000737:chemistry*
chemical_list: D007477:Ions; D008024:Ligands; D028561:Transition Elements