Topic
Shilov system
About: Shilov system is a research topic. Over the lifetime, 13 publications have been published within this topic receiving 226 citations.
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TL;DR: Mechanistic studies show that the originally proposed mechanism is incomplete and that while CH activation does proceed with Pt(II) there is a solution to the over-oxidation dilemma, and that increasing that rate could increase the rate of catalysis and catalyst stability.
Abstract: Designing oxidation catalysts based on CH activation with reduced, low oxidation state species is a seeming dilemma given the proclivity for catalyst deactivation by overoxidation. This dilemma has been recognized in the Shilov system where reduced PtII is used to catalyze methane functionalization. Thus, it is generally accepted that key to replacing PtIV in that system with more practical oxidants is ensuring that the oxidant does not over-oxidize the reduced PtII species. The “Periana-Catalytica” system, which utilizes (bpym)PtIICl2 in concentrated sulfuric acid solvent at 200 °C, is a highly stable catalyst for the selective, high yield oxy-functionalization of methane. In lieu of the over-oxidation dilemma, the high stability and observed rapid oxidation of (bpym)PtIICl2 to PtIV in the absence of methane would seem to contradict the originally proposed mechanism involving CH activation by a reduced PtII species. Mechanistic studies show that the originally proposed mechanism is incomplete and that wh...
72 citations
01 Jan 2011
TL;DR: The experimental and computational studies that have led to detailed mechanistic understanding of C-H activation and functionalization by both the original Shilov system and the many subsequent modifications that have been developed are discussed and the prospects for practical, selective catalytic oxidation of alkanes using this chemistry are assessed.
Abstract: The Shilov system, a mixture of di- and tetravalent chloroplatinate salts in aqueous solution, provided the first indication of the potential of organotransition metal complexes for activating and functionalizing alkanes under mild conditions; the participation of higher-valent species plays a crucial role. In this chapter, we discuss the experimental and computational studies that have led to detailed mechanistic understanding of C-H activation and functionalization by both the original Shilov system and the many subsequent modifications that have been developed, and assess the prospects for practical, selective catalytic oxidation of alkanes using this chemistry.
66 citations
TL;DR: The authors summarize 20+ years work on the mechanism of the Shilov system and related C-H activation chemistry and present a brief account of their personal encounters with Alex Shilev.
39 citations
TL;DR: In this paper, the activation of C-H bonds in mild conditions has been analyzed in the Shilov system, namely, platinum (II and (IV) halides in aqueous solution, has demonstrated the ability of homogenous catalysts to activate and functionalize saturated hydrocarbons including methane.
20 citations
TL;DR: In this article, a new Pt(II) ethyl ethene complex, [Pt(μ-Cl)(CH2CH3)(C2H4)]2, was isolated from the reaction of Ethene with K2PtCl4 in water, and the structure was confirmed by X-ray crystallography.
17 citations