Tailor-made Molecular Cobalt Catalyst System for the Selective Transformation of Carbon Dioxide to Dialkoxymethane Ethers
Herein a non-precious transition-metal catalyst system for the selective synthesis of dialkoxymethane ethers from carbon dioxide and molecular hydrogen is presented. The development of a tailored catalyst system based on cobalt salts in combination with selected Triphos ligands and acidic co-catalysts enabled a synthetic pathway, avoiding the oxidation of methanol to attain the formaldehyde level of the central CH2 unit. This unprecedented productivity based on the molecular cobalt catalyst is the first example of a non-precious transition-metal system for this transformation utilizing renewable carbon dioxide sources.
Schieweck, Benjamin G.,Klankermayer, Jürgen
supporting information
p. 10854 - 10857
(2017/08/30)
Ruthenium-Catalyzed Synthesis of Dialkoxymethane Ethers Utilizing Carbon Dioxide and Molecular Hydrogen
The synthesis of dimethoxymethane (DMM) by a multistep reaction of methanol with carbon dioxide and molecular hydrogen is reported. Using the molecular catalyst [Ru(triphos)(tmm)] in combination with the Lewis acid Al(OTf)3resulted in a versatile catalytic system for the synthesis of various dialkoxymethane ethers. This new catalytic reaction provides the first synthetic example for the selective conversion of carbon dioxide and hydrogen into a formaldehyde oxidation level, thus opening access to new molecular structures using this important C1source.
Thenert, Katharina,Beydoun, Kassem,Wiesenthal, Jan,Leitner, Walter,Klankermayer, Jürgen
supporting information
p. 12266 - 12269
(2016/10/13)
SYNTHESIS OF UNSYMMETRICAL 1,1-DIALKOXYALKANES AND THEIR SULFUR-CONTAINING ANALOGS
Acyclic acetals and 1,1-di(alkylthio)alkanes enter into exchange reactions in the presence of aprotic acids and of the KU-2 cation-exchange resin with the formation of the unsymmetric acetals and 1-alkoxy-1-alkylthioalkanes.In reaction with ethylal di(ethylthio)methane forms 3,5,7-trioxanonane in addition to ethylthioethoxymethane. 2-Methyl-4-thia-2-hexene was found in the products from the reaction of 1,1-di(ethylthio)-2-methylpropane with methylal.
Gazizova, L. B.,Imashev, U. B.,Musavirov, R. S.,Kantor, E. A.,Zlotskii, S. S.,et al.
p. 226 - 231
(2007/10/02)
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