Metal catalyzed oxidations. Part 2. Molybdenum catalyzed olefin epoxidation in nonpolar solvents11For Part 2 of the series: see [1].

Effect of an Ionic Liquid on the Catalytic Performance of Thiocyanatodioxomolybdenum(VI) Complexes for the Oxidation of Cyclooctene and Benzyl Alcohol

“…The infrared spectrum of this solid (2*) was very different from that for complex 2, and in fact [40][41][42]. These seven-coordinate molybdenum peroxo complexes are active catalysts for the epoxidation of olefins with TBHP, especially when L is a neutral bidentate N,N-ligand such as a substituted pyrazolylpyridine [40,43,44]. Mechanistic studies have indicated that the oxidising agent coordinates to the Mo VI centre, undergoes a proton transfer to one of the peroxo ligands and is activated for oxygen transfer by g 2 -coordination [45].…”

Nanoparticle Supported, Magnetically Recoverable Oxodiperoxo Molybdenum Complexes: Efficient Catalysts for Selective Epoxidation Reactions

“…As already observed for similar homogeneous oxodiperoxo molybdenum catalysts, the hetereogenized systems convert especially olefins without any functional groups attached. [19] This is due to the mechanism of the oxygen transfer. [17,20] For practical applications of heterogeneous catalyst systems, the stability and reusability are important factors.…”

Transition Metal Peroxides. Synthesis and Role in Oxidation Reactions*Dedicated, on the occasion of his 80th birthday, to our ‘vitae ac studiorum magister in secunda et in adversa fortuna’ Emeritus Professor Giorgio Modena, Padova University, who showed us the way toward Chemistry.

“…Long-chain derivatives of pyrazolyl pyridines coordinated to MoO(O 2 ) 2 as 35 may efficiently replace the conventional Mo(CO) 6 in the oxidation of several double-bond typologies with TBHP, in non-polar hydrocarbon solvents 244,245 . The epoxidation of cyclopentene and 2,3-dimethyl-2-butene led to the corresponding epoxides, notoriously sensitive to ring opening, in 100% and 87% yield respectively, in isoctane, with 1 hour reaction time.…”