Spectroscopic Characterization of a Copper(III) Trisuperoxide Complex Bearing Both Side-On and End-On Ligands

Abstract

The copper atom reacts with dioxygen in solid argon to form a mononuclear copper dioxygen complex Cu(eta(2)-O(2))(eta(1)-O(2))(2) bearing both side-on and end-on bonded O(2) ligands. The complex is characterized as being a trisuperoxide species with the copper center in its unusual +3 oxidation state. The Cu(III) trisuperoxide complex loses an end-on bonded superoxo ligand in forming the copper bisdioxygen complex under infrared irradiation.

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. [55] Ozonide complexes have been prepared for Sc, [45,46] Y, [47] La, [47] Cu, [99] Ag, [100] Zn, [104] and Cd.…”

“…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 …”

Oxygen, sulfur, selenium, tellurium and polonium

“…52 The newly synthesised ansa complexes [{k 1 -Sn t Bu 2 Sn t Bu 2 (Z 5 -C 5 H 4 )}(CO) 3 M] (M = Mo, W) are highly strained at the ansa bridge and readily react with chalcogens (E = S, Se, Te) via insertion of the chalogen into the Sn-Sn bond to give 5-7. 53 Reaction of Sn[N(SiMe 3 ) 2 ] 2 with 1,2-benzenedithiol (2 : 1 ratio) was reported to form the distannylene (8) which readily decomposed to form (9). In contrast, the reaction of Sn[N(SiMe 3 ) 2 ] 2 with catechol (3 : 2 ratio) gives tri-stannylene (10) which is stable in both solid and solution state.…”

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

“…It was characterized to be a trisuperoxide Cu 3+ (O 2 À ) 3 complex bearing both side-on and end-on bonded ligands. 33 In this paper, we provide a joint matrix isolation infrared spectroscopic and theoretical study of the formation and characterization of some oxygen-rich copper-oxygen complexes in solid argon. A CuO 5 species is characterized to be a superoxo copper ozonide complex.…”