Formation and characterization of the CuO5, CuO4 and CuO4− complexes in solid argon

Abstract

Matrix isolation infrared spectra and quantum chemical calculations of the copper dioxygen/ozonide complexes, CuO(5), CuO(4) and CuO(4)(-) are reported. These oxygen-rich species were prepared by reactions of laser-evaporated copper atoms with dioxygen or ozone in solid argon. The CuO(5) complex was determined to be a superoxo copper ozonide complex, in which both the superoxo and ozonide ligands are side-on bonded to the copper center. It was predicted to have a (4)A(1) ground state with planar C(2v) symmetry. Besides CuO(5), the previously observed CuO(4) complex and a new CuO(4)(-) anion were also formed. The CuO(4) complex was characterized to be a side-on bonded copper disuperoxide complex, which has a (4)B(2u) ground state with planar D(2h) symmetry. The CuO(4)(-) anion was characterized to be a disuperoxide complex with both superoxide ligands coordinated to the Cu center in an end-on fashion having a (3)A(u) ground state with planar C(2h) symmetry.

Metal Cluster Models for Heterogeneous Catalysis: A Matrix‐Isolation Perspective

“…There are also complexes of the metal atoms with one or more O 2 units, mostly superoxides, namely complexes with one O 2 for M = Rh, [86] Ni, [91,94,95] Pd, [92,93,98] Pt, [92,93,94] Cu, [99] Ag, [93,100] and Au, [93,100] and complexes with two O 2 units for M = Sc, [45,46,48] Y, [49] Rh, [81,86] Ni, [91] Pd, [92,93,98] Pt, [92,93] Cu, [101,102] and Ag. [44] For Sc, [48] Hf, [55] Rh, [86] and Cu [101] there are complexes with three O 2 units, and for Hf, there is even the Hf(O 2 ) 4 complex.…”

“…For all transition metals (except Tc), metal oxide particles have been generated and spectroscopically characterized in inert gas matrices and reviewed by Gong et al in 2009 . The oxides were generally produced by laser ablation of metals, thermal evaporation of metals, or by laser ablation of metal oxides . The monoxides MO have been generated for all transition metals except for M=Re, Os, and Pd.…”

“…Reactions of metal clusters have been studied with O 2 , N 2 , CO, N 2 O and H 2 O . There are only a few examples for reactions of clusters with organic molecules …”

Synthesis of Mesoporous Copper Aluminosilicate Hollow Spheres for Oxidation Reactions

“…Observing similar XANES spectra in the edge region as well as approximately identical CNs computed for both CuSi HS and our CASHS materials instigated uncertainty to the obtained results. First, it should be noted that, based on the literature reports, the deliberate formation of the pure CuO 5 conformation was already reported though under specific reaction environments . A report also characterized the features and differences of CuO 4 and CuO 5 conformations with the aid of density functional theory .…”

“…First, it should be noted that, based on the literature reports, the deliberate formation of the pure CuO 5 conformation was already reported though under specific reaction environments. 45 A report also characterized the features and differences of CuO 4 and CuO 5 conformations with the aid of density functional theory. 46 The authors pointed out in their study that experimental probes may not be fully capable to convey unambiguous geometries and bonding distances of various Cu moieties such as CuO 4 and CuO 5 .…”