Reductive Trimerization of CO to the Deltate Dianion Using Activated Magnesium(I) Compounds

• DOI: 10.1021/jacs.9b04085
• Publication Date: 2019-05-17T01:05:17Z
• Authors: K. Yuvaraj; Iskander Douair; Albert Paparo; Laurent Maron; Cameron Jones
• Keywords: Organometallic Chemistry; Reductive elimination

This study details syntheses of unsymmetrical magnesium(I)-adduct complexes, [(ArNacnac)(D)Mg-Mg(ArNacnac)] (ArNacnac = [(ArNCMe)2CH]-), Ar xylyl (Xyl), mesityl (Mes), 2,6-diethylphenyl (Dep), or 2,6-diisopropylphenyl (Dip); D N-heterocyclic carbene 4-dimethylaminopyridine, DMAP), which X-ray crystallographic studies show to have markedly elongated Mg-Mg bonds. Two these highly reactive species are shown reductively trimerize CO yield rare crystallographically characterized examples the planar, aromatic deltate dianion, incorporated in complexes [{(DipNacnac)(D)Mg(μ-C3O3)Mg(DipNacnac)}2] (D DMAP :C{N(Me)C(Me)}2). DFT calculations suggest that form via stepwise two-electron reductions three molecules, resulting formation C-C bonds within cyclic unit. work highlights utility activated magnesium(I) adduct as soluble organometallic models for reductive bond-forming events in, example, heterogeneously catalyzed Fischer-Tropsch process.