The water soluble Ni bis(diphosphine) complex [NiL2](BF4)2 (L = 1,2-
bis(di(methoxypropyl)phosphino)ethane) and the corresponding hydride, [HNiL2]BF4, were synthesized and characterized. For HNiL2+, the hydricity was determined to be 23.2(3) kcal/mol in aqueous solution. Based on the hydricity of formate of 24.1 kcal/mol, the transfer of a hydride from HNiL2
+ to CO2 to produce formate is favorable by 1 kcal/mol. Starting from either NiL2 2+ or HNiL2 + in water, catalytic hydrogenation of CO2 was observed with NaHCO3 (0.8 M) as the only additive. A maximum turnover frequency
of 3.6(8) h–1 was observed at 80 °C and 51 atm of a 1:1 mixture of CO2 and H2.
Revised: April 27, 2020 |
Published: April 7, 2017
Citation
Burgess S.A., A.J. Kendall, D.R. Tyler, D.R. Tyler, J.C. Linehan, and A.M. Appel. 2017.Hydrogenation of CO2 in Water Using a Bis(Diphosphine) Ni–H Complex.ACS Catalysis 7, no. 4:3089-3096.PNNL-SA-123128.doi:10.1021/acscatal.7b00350