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

• Published in: ChemistryOpen (Weinheim) 2019-12, Vol.8 (12), p.1453-1459
• Main Authors: Pascher, Tobias F., Ončák, Milan, Linde, Christian, Beyer, Martin K.
• Format: Article
• Language: English
• Subjects: calcination process; Carbon dioxide; Clusters; Coordination compounds; Copper compounds; copper hydrides; Copper oxides; Cupric formate; Decarboxylation; Decomposition; Decomposition reactions; Formic acid; Hydrides; Hydrogen atoms; Investigations; mass spectrometry; Morphology; Nitrates; Organic chemistry; Oxidation; Oxygen; Quantum chemistry; reaction mechanisms; Redox reactions; Roasting; Theory; Valence; Vapor phases
• ISSN: 2191-1363; 2191-1363
• DOI: 10.1002/open.201900282

The decomposition of copper formate clusters is investigated in the gas phase by infrared multiple photon dissociation of Cu(II)n(HCO2)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)(HCO2)2 or Cu(II)2(HCO2)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(HCO2)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)(HCO2)2− and Cu(II)(HCO2)3−, respectively, is unreactive towards oxygen. Calcination and carbon dioxide activation: Mass spectrometry provides fundamental insight into the complex mechanisms in thermal decomposition of copper formate, with and without the presence of oxygen, which are relevant for the calcination of copper salts and for hydrogen storage applications involving copper hydride‐based catalysts.