68332-58-1Relevant academic research and scientific papers
Application of Hetero-Triphos Ligands in the Selective Ruthenium-Catalyzed Transformation of Carbon Dioxide to the Formaldehyde Oxidation State
Seibicke, Max,Siebert, Max,Siegle, Alexander F.,Gutenthaler, Sophie M.,Trapp, Oliver
, p. 1809 - 1814 (2019)
Due to the increasing demand for formaldehyde as a building block in the chemical industry as well as its emerging potential as feedstock for biofuels in the form of dimethoxymethane and the oxymethylene ethers produced therefrom, the catalytic transformation of carbon dioxide to the formaldehyde oxidation state has become a focus of interest. In this work, we present novel ruthenium complexes with hetero-triphos ligands, which show high activity in the selective transformation of carbon dioxide to dimethoxymethane. We substituted the apical carbon atom in the backbone of the triphos ligand platform with silicon or phosphorus and optimized the reaction conditions to achieve turnover numbers as high as 685 for dimethoxymethane. The catalytic systems could also be tuned to preferably yield methyl formate with turnover numbers of up to 1370, which in turn can be converted into dimethoxymethane under moderate conditions.
Synthesis, immobilization, MAS and HR-MAS NMR of a new chelate phosphine linker system, and catalysis by rhodium adducts thereof
Guenther,Reibenspies,Bluemel
scheme or table, p. 443 - 460 (2011/04/16)
A new class of tridentate phosphine ligands with the general formula [MeP{(CH2)xPPh2}3]+I - (x=4, 7, 11) and [MeP(CH2PPh2) 3]+OTf-, has been synthesized and fully characterized. The linkers have been immobilized on silica with their phosphonium moieties via electrostatic interactions, and their mobility and leaching has been studied by solid-state HR-MAS (high-resolution magic angle spinning) NMR in various solvents. Immobilized Wilkinson-type rhodium complexes have been obtained by ligand exchange with the surface-bound linkers. The activities and lifetimes of the catalysts have been tested with respect to the hydrogenation of 1-dodecene. The rhodium catalyst precursor bound by the immobilized linker [MeP{(CH2)7PPh2} 3]+I- led to material with the highest activity and lifetime, and it could be recycled for 30atimes in a batchwise manner. The other catalysts show shorter lifetimes. For all catalysts the formation of rhodium nanoparticles with a narrow size distribution around 4anm has been proven.
