Ligand assisted carbon dioxide activation and hydrogenation using molybdenum and tungsten amides

The hepta-coordinated isomeric M(NO)Cl3(PN(H)P) complexes {M = Mo, ; W, , PN(H)P = (iPr2PCH2CH2)2NH, (HN atom of PN(H)P syn and anti to the NO ligand)} and the paramagnetic species M(NO)Cl2(PN(H)P) (M = Mo, ; W, ) could be prepared via a new synthetic pathway. The pseudo trigonal bipyramidal amides M(NO)(CO)(PNP) {M = Mo, ; W, ; [PNP](-) = [(iPr2PCH2CH2)2N](-)} were reacted with CO2 at room temperature with CO2 approaching the M[double bond, length as m-dash]N double bond in the equatorial (CO,NO,N) plane trans to the NO ligand and forming the pseudo-octahedral cyclic carbamates M(NO)(CO)(PNP)(OCO) (M = Mo, ; W = ). DFT calculations revealed that the approach to form the isomer is kinetically determined. The amine hydrides M(NO)H(CO)(PN(H)P) {M = Mo, ; W, }, obtained by H2 addition to , insert CO2 (2 bar) at room temperature into the M-H bond generating isomeric mixtures of the η(1)-formato complexes M(NO)(CO)(PN(H)P)(η(1)-OCHO), (M = Mo, ; M = W, ). Closing the stoichiometric cycles for sodium formate formation the isomeric mixtures were reacted with 1 equiv. of Na[N(SiMe3)2] regenerating . Attempts to turn the stoichiometric formate production into catalytic CO2 hydrogenation using in the presence of various types of sterically congested bases furnished yields of formate salts of up to 4%.