Activation of Bis(trimethylsilyl) Peroxide and tert‐Butyl Hydroperoxide with Oxo and Peroxo Complexes of Vanadium, Molybdenum, and Tungsten for the Sulfoxidation of Thianthrene 5‐Oxide

Abstract

Bis(trimethylsily1) peroxide (BTSP) and tert-butyl hydroper-as oxygen source were achieved with the vanadates oxide (tBuOOH) were activated by various 0x0 and peroxo [VO(OR),] (R = fBu, iPr). Comparative selectivity and rate complexes of molybdenum, tungsten, and vanadium as cata-data for the stoichiometric and catalytic sulfoxidations of SSO lysts for the sulfoxidation of thianthrene 5-oxide (SSO). A mediated by the Mo0,L complex ( L = OPtBu:,, OPnOct3, screening of a number of phosphane oxide and amine oxide ONnBu,, ONnOct,) suggest that the bisperoxo metal comligands revealed that BTSP was most efficiently activated by plex is the active oxygen transfer species. the [MoO5(0PfBu3)] complex. The best results for tBuOOH Clrem.

A density functional theory investigation of the bromide oxidation mechanism by a vanadium bromoperoxidase model complex

“…7, 8). The free energy barriers for TS (31) and TS (33) are in good agreement with the results for the same system obtained by Pecoraro et al [17]. Moreover, the decrease in the Br-O 2 bond distance of R3 (Figs.…”

“…4) and the analysis of the imaginary normal modes show that in the oxotransfer step (classic S N 2 mechanism), the attack of the Brand the cleavage of the O 2 -O 3 bond occurred simultaneously. The Br-O 2 -O 3 angle is nearly 180°, except for TS (31) and TS (33), in which the decrease in this angle due to a weak electrostatic interaction between Br -and vanadium, causing Br -to move towards the metal centre.…”

“…Optimisation of the HOBr group close to the [V(O) 2 -(Hheida)] complex (3) led to three different products (P1, P2 and P3, Scheme 1). The quantum mechanical calculations clarify the nature of the electrophilic or nucleophilic attack, which is generally discussed in oxygen transfer catalysis [33]. The analysis of the atomic charges indicates that the reaction takes place through a nucleophilic attack of the bromide on the hydroxyl group.…”

Peroxomolybdenum Complexes as Epoxidation Catalysts in Biphasic Hydrogen Peroxide Activation: Raman Spectroscopic Studies and Density Functional Calculations

“…[15] We found, however, that only an increase in the solubility of the complex in organic solvents, but not an increase in the phosphane oxide cone angle, had any catalytic acceleration effect. Complexes of the commercially available surfactant OPnOct 3 (4) were grown.…”

“…The following compounds were commercially available or prepared as described in the literature: NnDodec 3 (Merck), OPnOct 3 (Fluka), OPnDodec 3 , [41] OPtBu 3 , [42] AsnDodec 3 , [43] iPr 2 PCH 2 CH 2 OMe, [44] iPr 2 AsCH 2 CH 2 OMe, [45] [MoO 5 (OPtBu 3 )], [15] [MoO 5 (hmpa)(H 2 O)], [1] [ [1] Ligands OEnDodec 3 (E N, As): To amine or arsane EnDodec 3 (1 equiv) dissolved in diethyl ether, aqueous hydrogen peroxide (30 %; 5 equiv) was added dropwise. The mixture was stirred for three days at 30 8C (amine)/3 h at 25 8C (arsane).…”