title: Activation of CO by Hydrogenated Magnesium(I) Dimers: Sterically Controlled Formation of Ethenediolate and Cyclopropanetriolate Complexes.
abstract: This study details the formal hydrogenation of two magnesium(I) dimers {(Nacnac)Mg}2 (Nacnac = [{(C6H3R2-2,6)NCMe}2CH](-); R = Pr(i) ((Dip)Nacnac), Et ((Dep)Nacnac)) using 1,3-cyclohexadiene. These reactions afford the magnesium(II) hydride complexes, {(Nacnac)Mg(μ-H)}2. Their reactions with excess CO are sterically controlled and lead cleanly to different C-C coupled products, viz. the ethenediolate complex, ((Dip)Nacnac)Mg{κ(1)-O-[((Dip)Nacnac)Mg(κ(2)-O,O-O2C2H2)]}, and the first cyclopropanetriolate complex of any metal, cis-{((Dep)Nacnac)Mg}3{μ-C3(H3)O3}. Computational studies imply the CO activation processes proceed via very similar mechanisms to those previously reported for related reactions involving f-block metal hydride compounds. This work highlights the potential magnesium compounds hold for use in the "Fischer-Tropsch-like" transformation of CO/H2 mixtures to value added oxygenate products.
authors.affiliation: †School of Chemistry, Monash University, PO Box 23, Melbourne, Victoria 3800, Australia.
authors.forename: Ralte
authors.initials: R
authors.lastname: Lalrempuia
authors.affiliation: ‡Université de Toulouse et CNRS, INSA, UPS, UMR 5215, LPCNO, 135 Avenue de Rangueil, F-31077 Toulouse, France.
authors.forename: Christos E
authors.initials: CE
authors.lastname: Kefalidis
authors.affiliation: †School of Chemistry, Monash University, PO Box 23, Melbourne, Victoria 3800, Australia.
authors.forename: Simon J
authors.initials: SJ
authors.lastname: Bonyhady
authors.affiliation: †School of Chemistry, Monash University, PO Box 23, Melbourne, Victoria 3800, Australia.
authors.forename: Benedikt
authors.initials: B
authors.lastname: Schwarze
authors.affiliation: ‡Université de Toulouse et CNRS, INSA, UPS, UMR 5215, LPCNO, 135 Avenue de Rangueil, F-31077 Toulouse, France.
authors.forename: Laurent
authors.initials: L
authors.lastname: Maron
authors.affiliation: †School of Chemistry, Monash University, PO Box 23, Melbourne, Victoria 3800, Australia.
authors.forename: Andreas
authors.initials: A
authors.lastname: Stasch
authors.affiliation: †School of Chemistry, Monash University, PO Box 23, Melbourne, Victoria 3800, Australia.
authors.forename: Cameron
authors.initials: C
authors.lastname: Jones