Reaction of sulphides with acyl nitrates; a simple and rapid method for preparing sulphoxides

Preparative and kinetic study on the mechanisms of isomerization of square-planar complexes. Kinetic evidence for pseudorotation of a five-coordinate intermediate

“…The previously published trans to cis isomerization for PtCl2(PEt3)2 should read cis to trans. 12 Isomerization in the platinum-halide-phosphine squareplanar systems tends to proceed when a stable five-coordinate intermediate can be formed. This important conclusion can be drawn from Table I since it seems to be quite general that on addition of phosphine to cis-and trans-PtX2L2, PtXL3+ is formed in the polar solvent methanol, while PtX2L3 is formed in the nonpolar solvent pentane-10% dichloromethane.…”

Equilibrium thermodynamics and mechanism of cis-trans isomerization for diazidobis(methyldiphenylphosphine)palladium(II) and diazidobis(dimethylphenylphosphine)palladium(II)

“…This seems unlikely. 46 It is known that the chloro complexes do isomerize via an ionic mechanism in combination with the nonionic mechanism,6'11 and the tetrazolate complexes follow a nonionic mechanism when uncatalyzed and an ionic mechanism when catalyzed.7 This indicates that both routes are viable possibilities for isomerization, and whichever mechanism will prevail depends intimately upon the nature of the phosphine, Isomerization mechanisms for the phosphine-catalyzed (process A) and the uncatalyzed (process B) cis-trans isomerizattons of the complexes (R3P)2PdX2. For the complexes studied here, i.e., X -N3", process B seems to occur in all cases.…”

A Concise Review on Synthesis of Sulfoxides and Sulfones with Special Reference to Oxidation of Sulfides

“…However, the main drawback associated with the use of nitric acid is the possibility of concomitant nitration of the substrate or other side reactions. Few other oxides of nitrogen employed for the oxidation of sulfides are: acyl nitrates [63], nitroniumhexafluorophosphate [64], thallium nitrate [65], ceric ammonium nitrate [66], nitrogen tetroxide [67], polyvinylpyrrolidine supported dinitrogen tetroxide (PVP-N2O4) (Scheme 10) [68] etc.…”