Homogeneously catalysed reduction of carbon dioxide with silanes: a study on solvent and ligand effects and catalyst recycling

Umwandlung von Kohlendioxid mit Übergangsmetall‐Homogenkatalysatoren: eine molekulare Lösung für ein globales Problem?

“…[133] Zahlrei- den. [140,[145][146][147] [148] kann aber in Abhängigkeit vom Katalysator und seiner Koordinationssphäre durchaus variieren: Theoretische Untersuchungen zeigten, dass der zweite Mechanismus ebenfalls mçglich ist. [149] [152][153][154][155][157][158][159][160][161][162][163][164][165] 1992 berichteten Nicholas und Tsai [151] sowie Leitner und Graf [152] Die Insertion von CO 2 in M-O-Bindungen führt zur Bildung von Carbonatspezies an Metallzentren.…”

Mechanism of olefin hydrosilylation catalyzed by [RuCl(NCCH3)5]+: A DFT study

“…The cation C1 is produced as an ion pair [20,21] -trans-[Ru II Cl(MeCN) 5 ][Ru III Cl 4 (MeCN) 2 ] -with a Ru(II) cation and a Ru(III) anion, from the reaction of RuCl 3 with dimethylphenylsilane in acetonitrile. As mentioned before, we only consider the Ru(II) cation C1 as catalyst for the hydrosilylation reaction.…”

“…Nonetheless, some very selective ruthenium catalysts have been found for the regioselective hydrosilylation of alkynes, especially the cationic ruthenium species [Cp * Ru(NCMe) 3 ]PF 6 which has been extensively used by Trost and Ball [13,14]. Another ionic 2 ] has been shown to be a very effective catalyst in the hydrosilylation of CO 2 with tri-and diorganosilanes [20,21]. These studies prompted us to investigate the activity of the latter catalyst in the hydrosilylation of C@C-functional substrates.…”

Catalytic synthesis of silyl formates with 1 atm of CO2 and their utilization for synthesis of formyl compounds and formic acid

“…Hydrosilanes are readily available, easy-to-handle, nontoxic, and inexpensive reducing agents [12,13], and the reduction of CO 2 with hydrosilanes to produce silyl formates [14][15][16][17][18][19][20][21], formaldehyde [22], methoxysilanes [23][24][25], and methane [26,27] is thermodynamically favorable. In particular, methoxysilanes [23][24][25] and methane [26] have been obtained in 1 atm of CO 2 .…”

“…In addition, it is expected that silyl formates can be regarded as "formyl synthons" due to their strong Si O bonds and that various kinds of carbonyl compounds can possibly be synthesized by the reaction with the corresponding nucleophiles. However, the synthesis of silyl formates from CO 2 itself generally requires high pressure of CO 2 (≥3 atm) (Table S1) [14][15][16][17][18][19][20]. In contrast, Sattler and Parkin quite recently realized the hydrosilylation of 1 atm of CO 2 using [Tris(2-pyridylthio)methyl]zinc hydride [21].…”