Epoxidation of Olefins by Water Oxygen Catalyzed by Platinum Blue Complexes

Abstract

The first olefin epoxidation by water oxygen is reported. The reaction is catalyzed by platinum blue complexes and is the first example that water oxygen atom is introduced into epoxides in catalytic or stoichiometric reaction.

Electrophilic Activation of Alkenes by Platinum(II): So Much More Than a Slow Version of Palladium(II)

“…Matsumoto and co-workers [88,89] reported that tetranuclear platinum blue complexes and dinuclear Pt …”

Catalytic Olefin Epoxidation With Molecular Oxygen Over Supported Amidate-Bridged Platinum Blue Complexes

“…All the supported catalysts showed much higher catalytic activity than those of our earlier reported soluble platinum complexes in aqueous-organic biphasic solutions. 2, 16 It is especially noteworthy that styrene was not epoxidized in the previous biphasic solution reactions, but is epoxidized in the present supported system in good yield. And also the reaction proceeds much faster in the present system.…”

“…8,13 Although amidate-bridged platinum(III) complexes catalyze the oxidation of olefins in biphasic aqueous-organic solutions, only cyclic olefins can be epoxidized with low turnover number (less than 25 moles of epoxides per mole of platinum blue complexes). 16 The true active catalyst in the reactions was found to be the platinum(III) dimer complex produced from the oxidation of the platinum blue complex. 2 By extending these our earlier results on the organometallic and catalytic chemistry of platinum blue complexes, here we report the immobilization of the platinum blue complexes on SiO 2 , Al 2 O 3 , activated carbon, and poly(4-vinylpyridine), and their catalytic properties for the expoxidation of various olefins in the presence of a sacrificial aldehyde under atmospheric pressure of molecular oxygen at room temperature.…”

Axial ligand effect on the reaction mechanism of head-to-head pivalamidato-bridged Pt(III) binuclear complex containing an equatorial bromide ligand with acetone

“…One of these is coordinated by two ammine nitrogen and two amidate oxygen atoms (Pt(N 2 O 2 )), whereas the other is coordinated by two ammine and two amidate nitrogen atoms (Pt(N 4 )) and Pt(N 2 O 2 ) and Pt(N 4 ) are connected by a Pt-Pt bond [1]. These complexes act as catalysts in the oxidation reactions of olefins to aldehydes, ketones, epoxides, and a,b-diols [2][3][4][5]. In a series of studies on the reaction mechanisms of amidato-bridged Pt III binuclear complexes with organic compounds, we have reported the mechanisms of their reactions with olefins [6,7], phenol [8], isoprene [9], and acetone [10] in acidic aqueous solutions.…”