Redox Reactions of Nickel, Copper, and Cobalt Complexes with 'Noninnocent' Dithiolate Ligands: Combined in Situ Spectroelectrochemical and Theoretical Study

Autor:	Jozef Kozisek, Peter Machata, Karol Lušpai, Lukas Bucinsky, Stanislava Šoralová, Peter Herich, Martin Breza, Peter Rapta
Rok vydání:	2014
Předmět:	Chemistry Ligand Organic Chemistry Inorganic chemistry chemistry.chemical_element Redox Copper law.invention Inorganic Chemistry Nickel Crystallography law Singlet state Physical and Theoretical Chemistry Cyclic voltammetry Electron paramagnetic resonance Cobalt
Zdroj:	Organometallics. 33:4846-4859
ISSN:	1520-6041 0276-7333
DOI:	10.1021/om5000584
Popis:	The redox properties of copper, nickel, and cobalt complexes (MePh3P)[M(bdt)2] with the ligand benzene-1,2-dithiolate (bdt) and synthesized complexes (MePh3P)[M(bdtCl2)2] with the ligand 3,6-dichlorobenzene-1,2-dithiolate (bdtCl2) have been studied by cyclic voltammetry and in situ EPR–UV/vis/NIR spectroelectrochemistry. The addition of chlorine substituents to the 3- and 6-positions of the benzene ring not only facilitates the reduction of [M(bdtCl2)2]− complexes but also leads to the remarkable stabilization of [M(bdtCl2)2]2– dianions in solution. In contrast to the EPR-silent copper complexes, the solutions of nickel samples exhibit a broad singlet EPR signal at room temperature which becomes anisotropic at 100 K with a characteristic rhombic pattern. Cathodic reduction of copper and cobalt complexes leads to paramagnetic species having an EPR signal with splitting from 63,65Cu for copper and from 59Co for cobalt samples, confirming a strong contribution of the central atom with substantial delocalizat...
Databáze:	OpenAIRE
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