Open AccessDecomposition of Copper Formate Clusters: Insight into Elementary Steps of Calcination and Carbon Dioxide Activation
Author(s) -
Pascher Tobias F.,
Ončák Milan,
Linde Christian,
Beyer Martin K.
Publication year - 2019
Publication title -
chemistryopen
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.644
H-Index - 29
ISSN - 2191-1363
DOI - 10.1002/open.201900282
Subject(s) - calcination , carbon dioxide , copper , decomposition , formate , chemistry , inorganic chemistry , chemical engineering , organic chemistry , catalysis , engineering
The decomposition of copper formate clusters is investigated in the gas phase by infrared multiple photon dissociation of Cu(II) n (HCO 2 ) 2 n +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.