title: Synthesis of ruthenium(II) complexes containing hydroxymethylphosphines and their catalytic activities for hydrogenation of supercritical carbon dioxide.
abstract: Ligand substitution of RuCl2[P(C6H5)3]3 and Cp*RuCl(isoprene) (Cp*=1,2,3,4,5-pentamethylcyclopentadienyl) complexes with hydroxymethylphosphines was investigated to develop new catalyst systems for CO2 hydrogenation. A reaction of P(C6H5)2CH2OH with RuCl2[P(C6H5)3]3 in CH2Cl2 gave Ru(H)Cl(CO)[P(C6H5)2CH2OH]3 (1), which was characterized by NMR spectroscopy and X-ray crystallographic analysis. An isotope labeling experiment using P(C6H5)213CH2OH indicated that the carbonyl moiety in complex 1 originated from formaldehyde formed by degradation of the hydroxymethylphosphine. Elimination of formaldehyde from PCy2CH2OH (Cy=cyclohexyl) was also promoted by treatment of RuCl2[P(C6H5)3]3 in ethanol to give RuCl2(PHCy2)4 under mild conditions. On the other hand, the substitution reaction using Cp*RuCl(isoprene) with the hydroxymethylphosphine ligands proceeded smoothly with formation of Cp*RuCl(L)2 [2a-2c; L=P(C6H5)2CH2OH, PCy(CH2OH)2, and P(CH2OH)3] in good yields. The isolable hydroxymethylphosphine complexes 1 and 2 efficiently catalyzed the hydrogenative amidation of supercritical carbon dioxide (scCO2) to N,N-dimethylformamide (DMF).
authors.affiliation: Department of Applied Chemistry, Graduate School of Science and Engineering, Tokyo Institute of Technology, 2-12-1 O-okayama, Meguro-ku, Tokyo 152-8552, Japan.
authors.forename: Yoshihito
authors.initials: Y
authors.lastname: Kayaki
authors.forename: Yoshiki
authors.initials: Y
authors.lastname: Shimokawatoko
authors.forename: Takao
authors.initials: T
authors.lastname: Ikariya