Chelate complex Ni(S2C2H2)2 as a molecular model of the hydrodesulfurization active center

Abstract

Electronic states of Ni atom in a square-planar complex Ni(S2C2n2)2 and its molecular adduct with H2S were studied by means of ab initio molecular orbital calculations. H2S adsorption stabilizes the Ni(IV) state (d 6) ill the complex with the Ni atom shifted from the plane by 0.35

Oxidative addition of dihydrogen to Ni(II) complexes.ab initio MO/MP4 calculations of the electronic structure of NiH2Cl2(PH3)2 complex

“…Accounting for the tendency of the Ni(S2CzR2)2 complex to form stable dimeric structures, one can assume [25] that these are structures for which the unusual Ni(IV) oxidation state with electron configuration d 6 can occur. Our ab initio calculations of the H2S -Ni(SECEHz)z molecular adduct have confirmed stabilization of the Ni(IV) species [26].…”

Syntheses of Metal Dithiolene Complexes from Thiometalates by Induced Internal Redox Reactions

“…17,18 Nickel bis(dithiolene) complexes have been used as molecular models for the nickel site in the active center of hydrodesulfurization catalysts. 19,20 The wide range of interest in this class of compounds has stimulated exploration of new methods to synthesize the complexes by convenient, high-yield reactions. [21][22][23][24][25][26] The concept of induced internal electron-transfer reactions was first systematically applied to coordination compounds by Taube.…”

“…Metal dithiolene complexes (metallo-1,2-enedithiolates) have attracted considerable attention since they were first reported. , While early interest focused primarily on the redox and optical properties of the complexes, − more recently the scope has expanded to areas ranging from bioinorganic chemistry to material science. Some dithiolene complexes have been reported as conducting − and magnetic materials; , others as solution lumophores. − It has been established that all molybdenum enzymes, except for nitrogenase, and all tungsten enzymes contain the pterin cofactor designated as Mo-co (or W-co) in which a metal−dithiolene structural motif is present. , Nickel bis(dithiolene) complexes have been used as molecular models for the nickel site in the active center of hydrodesulfurization catalysts. , The wide range of interest in this class of compounds has stimulated exploration of new methods to synthesize the complexes by convenient, high-yield reactions. − …”