A Dimetallic Aminonitrone Nickel(II) Complex: Further Insights into Metal‐Mediated Nucleophilic Activation of Amidoximes. Issue 30 (23rd October 2017)

• Record Type: Journal Article
• Authors: Bolotin, Dmitrii S.; Bikbaeva, Zarina M.; Novikov, Alexander S.; Suslonov, Vitalii V.; Bokach, Nadezhda A.
• Is Part Of: ChemistrySelect. Volume 2:Issue 30(2017)
• Page Start: 9674
• Page End: 9678
• Publication Date: 2017-10-23
• Subjects: amidoxime -- aminonitrone -- nitrone -- nucleophilic activation -- transition metal; Chemistry -- Periodicals; 540.5
• DOI: 10.1002/slct.201702232
• Languages: English
• ISSNs: 2365-6549

Abstract

Abstract: The reaction of NiCl2 2H2 O with acetamidoxime (MeC(NH2 )=NOH) in the presence of PhCN in MeOH gave the cationic dimetallic complex [1 ]Cl4, bearing bridging O ‐coordinated aminonitrone and chelating imidoylamidoxime ligands, derived from amidoxime‐PhCN coupling. The experimental data and theoretical calculations (M06/MDF10(Ni) and 6–31G*(other atoms) indicated that the aminonitrone form of amidoxime was stabilized only as a μ 2 ‐ O ‐bridging ligand, whereas N oxime ‐coordination was preferred rather than O ‐coordination for monodentate‐coordinated amidoximes. Abstract : Acetamidoxime was stabilized in its aminonitrone form as a μ 2 ‐ O ‐bridging ligand in a dimetallic nickel(II) complex. Aminonitrone is supposed to be a reactive form of amidoximes in nucleophilic addition reactions. Theoretical calculations indicated the crucial role of two metal centres in the stabilization of the aminonitrone form, which is thermodynamically disadvantageous at a single nickel(II) centre.