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Decomposition of Copper Formate Clusters: Insight into Elementary Steps of Calcination and Carbon Dioxide Activation

The decomposition of copper formate clusters is investigated in the gas phase by infrared multiple photon dissociation of Cu(II)(n)(HCO(2))(2n+1) (−), n≤8. In combination with quantum chemical calculations and reactivity measurements using oxygen, elementary steps of the decomposition of copper form...

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Detalles Bibliográficos
Autores principales: Pascher, Tobias F., Ončák, Milan, van der Linde, Christian, Beyer, Martin K.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2019
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6916659/
https://www.ncbi.nlm.nih.gov/pubmed/31871848
http://dx.doi.org/10.1002/open.201900282
Descripción
Sumario:The decomposition of copper formate clusters is investigated in the gas phase by infrared multiple photon dissociation of Cu(II)(n)(HCO(2))(2n+1) (−), n≤8. In combination with quantum chemical calculations and reactivity measurements using oxygen, elementary steps of the decomposition of copper formate are characterized, which play a key role during calcination as well as for the function of copper hydride based catalysts. The decomposition of larger clusters (n >2) takes place exclusively by the sequential loss of neutral copper formate units Cu(II)(HCO(2))(2) or Cu(II)(2)(HCO(2))(4), leading to clusters with n=1 or n=2. Only for these small clusters, redox reactions are observed as discussed in detail previously, including the formation of formic acid or loss of hydrogen atoms, leading to a variety of Cu(I) complexes. The stoichiometric monovalent copper formate clusters Cu(I)(m)(HCO(2))(m+1) (−), (m=1,2) decompose exclusively by decarboxylation, leading towards copper hydrides in oxidation state +I. Copper oxide centers are obtained via reactions of molecular oxygen with copper hydride centers, species containing carbon dioxide radical anions as ligands or a Cu(0) center. However, stoichiometric copper(I) and copper(II) formate Cu(I)(HCO(2))(2) (−) and Cu(II)(HCO(2))(3) (−), respectively, is unreactive towards oxygen.