TY - JOUR
T1 - Activation of CO by hydrogenated magnesium(I) dimers
T2 - sterically controlled formation of ethenediolate and cyclopropanetriolate complexes
AU - Lalrempuia, Ralte
AU - Kefalidis, Christos E.
AU - Bonyhady, Simon James
AU - Schwarze, Benedikt
AU - Maron, Laurent
AU - Stasch, Andreas
AU - Jones, Cameron
N1 - Financial support from the Australian Research Council (C.J., A.S.), the U.S. Air Force Asian Office of Aerospace Research and Development (grant FA2386-14-1-4043 to C.J.), and the Alexander von Humboldt Foundation (grant of experienced researcher to L.M.), is acknowledged. Part of this research was undertaken on the MX1 beamline at the Australian Synchrotron, Victoria, Australia.
PY - 2015/7/22
Y1 - 2015/7/22
N2 - This study details the formal hydrogenation of two magnesium(I) dimers {(Nacnac)Mg}2 (Nacnac = [{(C6H3R2-2,6)NCMe}2CH]−; R = Pri (DipNacnac), Et (DepNacnac)) 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, (DipNacnac)Mg{κ1-O-[(DipNacnac)Mg(κ2-O,O-O2C2H2)]}, and the first cyclopropanetriolate complex of any metal, cis-{(DepNacnac)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.
AB - This study details the formal hydrogenation of two magnesium(I) dimers {(Nacnac)Mg}2 (Nacnac = [{(C6H3R2-2,6)NCMe}2CH]−; R = Pri (DipNacnac), Et (DepNacnac)) 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, (DipNacnac)Mg{κ1-O-[(DipNacnac)Mg(κ2-O,O-O2C2H2)]}, and the first cyclopropanetriolate complex of any metal, cis-{(DepNacnac)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.
U2 - 10.1021/jacs.5b06439
DO - 10.1021/jacs.5b06439
M3 - Article
SN - 0002-7863
VL - 137
SP - 8944
EP - 8947
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 28
ER -
