Structure of the product formed in the reaction of carbon dioxide with ruthenium hydride complexes

Synthesis and reactivity of [OsH{C6H4(CHCHH) }(CO)(PPri3)2] and the formato compounds [Os{(E )-CHCHPh}(η2-O 2CH)(CO)(PPri3)2] and [OsH(η2-O2CH)(CO)(PPri3) 2]*

“…7 The value of the asymmetric ν(OCO) stretching is very similar to that of 1565 cm Ϫ1 for [RuH(η 2 -O 2 CH)(PPh 3 ) 3 ], which contains a chelating formate ligand as confirmed by X-ray diffraction. 8 This value is also in agreement with those previously reported for the complexes Carbonylation of the bidentate formato complex 8 leads to formation of the monodentate formato derivative 9 (Scheme 8). The reaction was carried out in hexane, and complex 9 was isolated as a white solid in 83% yield.…”

Effect of Ligand Electronics on the Reversible Catalytic Hydrogenation of CO2 to Formic Acid Using Ruthenium Polyhydride Complexes: A Thermodynamic and Kinetic Study

“…Complexes of the type H 4 Ru­(PR 3 ) 3 are a representative subgroup of the larger family of Ru phosphine catalysts for CO 2 hydrogenation and are among the first reported by Inoue . The reaction of H 4 Ru­(PPh 3 ) 3 with CO 2 to form a κ 2 -formate complex, the key elementary step for the initial C–H bond formation, is rapid and nearly thermoneutral . Catalysts based on the related Ru­(triphos) system hydrogenate CO 2 to not only formate but also formaldehyde derivatives and even methanol .…”

Hydrogenation of carbon dioxide to methanol using a homogeneous ruthenium–Triphos catalyst: from mechanistic investigations to multiphase catalysis

“…[36][37][38] A [ 1 H, 13 C]-HMBC-NMR experiment showed the coupling of the proton signal at 8.7 ppm to a singlet at 178.8 ppm in the 13 C-NMR, further corroborating the formation of a formate-complex. 23,39,40 No hydride signals corresponding to this species were detected in the respective correlation NMR spectra.…”

“…FT-IR analysis of this solution at room temperature showed a n CO stretching mode at 1543 cm À1 , a typical value for h 2 -coordinated formate. [37][38][39][40] Based on these data and on the basis of literature precedence, 37 we assigned the structure of this complex as [(Triphos)Ru(h 2 -O 2 CH)(THF)] + (3a), where the weakly bound solvent molecule THF accounts for the uxionality at room temperature (Scheme 3).…”