31275-06-6Relevant academic research and scientific papers
Effect of Ligand Electronics on the Reversible Catalytic Hydrogenation of CO2 to Formic Acid Using Ruthenium Polyhydride Complexes: A Thermodynamic and Kinetic Study
Bordet, Alexis,Estes, Deven P.,Leitner, Walter,Leutzsch, Markus,Schubert, Lukas
, p. 2990 - 2998 (2020/03/23)
Hydrogenation of CO2 to formic acid or formates is often carried out using catalysts of the type H4Ru(PR3)3 (1). These catalysts are also active for the reverse reaction, i.e., the decomposition of formic acid to H2 and CO2. While numerous catalysts have been synthesized for reactions in both directions, the factors controlling the elementary steps of the catalytic cycle remain poorly understood. In this work, we synthesize a series of compounds of type H4Ru(P(C6H4R)3)3 containing both electron-donating and electron-withdrawing groups and analyze their influence on the kinetic and thermodynamic parameters of CO2 insertion and deinsertion. The data are correlated with the catalytic performance of the complexes through linear free-energy relationships. The results show that formic acid dissociation from the catalyst is rate-determining during CO2 hydrogenation, while deinsertion is critical for the decomposition reaction.
Catalysis of the hydrogenation of benzophenone by polyhydride complexes of tris(triphenylphosphine)ruthenium
Linn, Donald E. Jr.,Halpern, Jack
, p. 155 - 160 (2007/10/02)
The following reactions have been identified in THF solution (P=PPH3): (1) (3) + Ph2C=O -> (4) + Ph2CHOH. (2) 4 + H2 -> 3. (3) 4 + 2Ph2C=O -> H(O=CPhC6H4)P3> (5) + Ph2CHOH. (4) 5 + 2H2 -> 4 + Ph2CHOH. (5) - (1) + Ph2C=O -> 4 + Ph2CHO-. (6) 3 + Ph2CHO- -> 1 + Ph2CHOH.Each of the following combination of steps constitutes one of a set of interconnected catalytic cycles for the hydrogenation of Ph2C=O to Ph2CHOH: (1) + (2); (3) + (4); (2) + (6) + (5).
Roles of Neutral and Anionic Ruthenium Polyhydrides in the Catalytic Hydrogenation of Ketones and Arenes
Linn, Donald E.,Halpern, Jack
, p. 2969 - 2974 (2007/10/02)
fac-- (1) and (3) have been shown to coexist through the equilibrium 1 + ROH 3 + RO-, for which Keq ca. 0.13 for cyclohexanol in THF.The following reactions have been characterized: (1) 3 +
HYDRIDO(PHOSPHINE)RUTHENATE COMPLEXES AND THEIR ROLE IN THE CATALYTIC HYDROGENATION OF ARENES
Fordyce, William A.,Wilczynski, Robert,Halpern, Jack
, p. 115 - 126 (2007/10/02)
Starting with the potassium salt of (1), the following reactions in THF were identified: (1) 1+H2 -> fac-- (2); (2) 1+1,4-Ph2-1,3-butadiene -> - (3) + PPh3; (3) 3+4H2 -> - (4) + 1,4-Ph2-butane; (4) 4 + 1-hexene -> - (5) + hexane; (5) 4 + L -> - + H2 (L = CO, PPh3, PMe2Ph); (6) 2 + 1,5-anthracene (A) -> - (7) + 0.5 (1,2,3,4-H4A) + PPh3; (7) 4 + 5 C2H4 -> (8) + 3C2H6; (8) 4 + 2A -> 7 + 1,2,3,4-H4A; (9) 7 + 4H2 -> 4 + 1,2,3,4-H4A.Reactions 8 and 9 constitute a catalytic cycle for the hydrogenation of anthracene to 1,2,3,4-tetrahydroanthracene.
PREPARATION AND PROPERTIES OF GROUP 8 TRANSITION METAL ALKOXIDES RELEVANT TO CATALYTIC HYDROGENATION OF KETONES TO ALCOHOLS
Hayashi, Yoshinori,Komiya, Sanshiro,Yamamoto, Takakazu,Yamamoto, Akio
, p. 1363 - 1366 (2007/10/02)
Alkoxo complexes, M(OR)Ln and MH(OR)Ln (M=Co, Rh, Ru, L=PPh3; R=CH(CF3)2, CHPh(CF3)), have been prepared by insertion of fluoroketones into M-H bonds in CoH(N2)L3, RhHL4, and RuH2L4.Hydrogenolysis of the Ru- and Rh-alkoxo complexes w
SYNTHESIS AND 31P NMR SPECTRA OF SOME DIENE COMPLEXES OF IRON(O) AND RUTHENIUM(O) CONTAINING PHOSPHINE LIGANDS
Al-Ohaly, Abdul-Razzak,Nixon, John F.
, p. 297 - 308 (2007/10/02)
The preparation of the η4-butadiene complexes of zerovalent iron and ruthenium Ru(η4-C4H6)(PPh3)(L)2, (L=P(OCH2)3CMe, P(OMe)3, PF2NMe2, PF3); Fe(η4-C4H6)(CO)(L)2, (L=P(OMe)3, P(OCH2)3CMe), and the cyclohexadiene complexes
