Szilagyi, Robert K. Lim, Booyong S. Glaser, Thorsten Holm, Richard H. Hedman, Britt Hodgson, Keith O. Solomon, Edward I. Description of the Ground State Wave Functions of Ni Dithiolenes Using Sulfur K-edge X-ray Absorption Spectroscopy The pterin-dithiolene cofactor is an essential component of the catalytic sites of all molybdoenzymes except nitrogenase. Understanding its bonding to transition metals allows for development of electronic structure/function correlations in catalysis. The electronic structure description for a series of bis(dithiolene) complexes ([NiL<sub>2</sub>]<i><sup>Z</sup></i><sup></sup>, L = 1,2-Me<sub>2</sub>C<sub>2</sub>S<sub>2</sub>; <i>Z</i> = 2−, 1−, 0) using sulfur XAS provides the basis for extension to the biologically relevant metal-containing dithiolenes. The transition dipole integral has been developed for the dithiolene sulfur through correlation of XAS pre-edge energy positions of sulfide-, thiolate-, and enedithiolate-S. The ground state wave functions of all three NiL<sub>2</sub> complexes have more than 50% S character experimentally demonstrating the noninnocent behavior of the dithiolene ligand. The S K-edge experimental results are correlated with spin-unrestricted, broken-symmetry density functional calculations. These show only limited spin polarization in the neutral complex and delocalized, ligand based ground states for the mono- and dianionic complexes. These XAS and DFT results are correlated with other spectroscopic features and provide insight into reactivity. DFT results;sulfur XAS;structure description;ground states;NiL 2 complexes;dithiolene sulfur;transition metals;Ni Dithiolenes;Ground State Wave Functions;dithiolene ligand;ground state wave functions;spectroscopic features;2 C 2 S 2;noninnocent behavior;dianionic complexes;correlation 2003-07-04
    https://acs.figshare.com/articles/journal_contribution/Description_of_the_Ground_State_Wave_Functions_of_Ni_Dithiolenes_Using_Sulfur_K-edge_X-ray_Absorption_Spectroscopy/3648702
10.1021/ja029806k.s001