Reaction of a Redox-Active Ligand Complex of Nickel with Dioxygen Probes Ligand-Radical Character

Bis(imino)pyridine complex [Ni{2,6-(ArNCMe)2C5H3N}Cl] (where Ar = 2,6- i Pr2C6H3) was synthesized by reduction of the corresponding dichloride complex and characterized as a ligand-radical complex of NiII. Reaction of this complex with O2 caused intraligand C−C bond cleavage to afford the Ni comple...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2009-11, Vol.131 (43), p.15582-15583
Main Authors: Manuel, Tony D, Rohde, Jan-Uwe
Format: Article
Language:English
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Summary:Bis(imino)pyridine complex [Ni{2,6-(ArNCMe)2C5H3N}Cl] (where Ar = 2,6- i Pr2C6H3) was synthesized by reduction of the corresponding dichloride complex and characterized as a ligand-radical complex of NiII. Reaction of this complex with O2 caused intraligand C−C bond cleavage to afford the Ni complex of the new iminoethylpyridylcarboxamidato ligand, which also was isolated as the corresponding carboxamide, 6-(ArNCMe)C5H3N-2-C(O)NHAr. This reaction serves as an example of small-molecule activation effected directly at the redox-active bis(imino)pyridine ligand without an overall oxidation state change at the Ni center.
ISSN:0002-7863
1520-5126
DOI:10.1021/ja9065943