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Correlated Coordination and Redox Activity of a Hemilabile Noninnocent Ligand in Nickel Complexes

Dipl.-Chem. Alexa Paretzki 1 ,  Dipl.-Chem. Martina Bubrin 1 ,  Dr. Jan Fiedler 2 ,  Dr. Stanislav Záliš 2  and Prof. Dr. Wolfgang Kaim 1,* Article first published online: 24 MAR 2014 DOI: 10.1002/chem.201304316 rServices Abstract Article References Supporting Information Cited By View Full Article with Supporting Information (HTML)   Enhanced Article (HTML)   Get PDF (885K) Keywords: coordination change; hemilabile ligands; nickel; noninnocent ligands; redox chemistry Abstract The compound [Ni(Q M ) 2 ], Q M =4,6-di- tert -butyl- N -(2-methylthiomethylphenyl)- o -iminobenzoquinone, is a singlet diradical species with approximately planar configuration at the tetracoordinate metal atom and without any Ni S bonding interaction. One-electron oxidation results in additional twofold Ni S coordination ( d Ni S ≈2.38 Å) to produce a complex cation of [Ni(Q M ) 2 ](PF 6 ) with hexacoordinate Ni II ...