Synthesis, Vibrational Spectra, and Single-Crystal X-ray Structure of the Phosphato-Bridged Dinuclear Peroxovanadate (NH4)5[V2O2(O2)4PO4].cntdot.H2O

A comparative DFT study on the mechanism of olefin epoxidation catalyzed by substituted binuclear peroxotungstates ([SeO4WO(O2)2MO(O2)2]n− (M = TiIV, VV, TaV, MoVI, WVI, TcVII, and ReVII))

“…Figure shows the corresponding reaction process. The optimization results of the reactant showed that the VO and OO bonds (VO1 = 1.932 Å, VO2 = 1.868 Å, VO3 = 1.860 Å, VO4 = 1.878 Å, O1O2 = 1.442 Å, and O3O4 = 1.444 Å) were comparable to those in the dinuclear peroxovanadate [V 2 O 2 (O 2 ) 4 PO 4 ] 5− according to X‐ray crystallography . The transition state search and the corresponding energy barrier for the first step in ethylene epoxidation were calculated, in which the CC double bond directly attacked the peroxo O groups in a spiro fashion .…”

“…The olefin epoxidation reaction is always described as a cycloaddition reaction in which a nucleophilic alkene is attacked by an electrophilic reagent. In other words, the transition metal peroxo complexes always behave as the electronphilic oxidants …”

Calcium and strontium salts of (glycinato-κ2N,O)oxidobis(peroxido-κ2O,O′)vanadate(V) tetrahydrate

“…(Svensson et al, 1971), in which V atoms are triply bridged by two peroxo groups and one oxo group, by removing the bridging oxo group to give positions for the coordination of the glycine ligand. The moiety is also related to [V 4 O 4 (O 2 ) 8 (PO 4 )] 7À (Schwendt et al, 1996) and [V 2 O 2 (O 2 ) 4 (PO 4 )] 5À (Schwendt et al, 1994), having so-called Ishii-Venturello and lacunary Ishii-Venturello-type structures, respectively, in which two V atoms are doubly bridged by two 1 , 2 -peroxo groups. The structure of (II) can be derived by replacing the phosphate group of the latter with glycine.…”

Mixed crystals containing the dioxo complex [{Ph3SiO}2VO2]−and novel pentacoordinated oxoperoxo complex [{Ph3SiO}2VO(O2)]−: X-ray crystal structure and assessment as oxidation catalysts

“…10 The only two cases of a pentagonal pyramidal geometry are for oxodiperoxovanadium complexes; 30-31 for the other complexes with pentagonal monopyramids, the oxygen atom of another molecule or even of another metal centre may well serve as the seventh ligand with a long axial bond. 32, 33 Complex 1b is the first pentacoordinate structure for a monooxoperoxo anion for which the coordination environment of the vanadium atom is severely distorted and is close to a trapezoidal pyramid, with the oxo group occupying the apical position; the base is the peroxo group and the oxygen atoms of the triphenylsilanolato ligands (Figs. 2 and 3).…”