|
The Shilov system is a classic example of catalytic C-H bond activation and oxidation which preferentially activates stronger C-H bonds over weaker C-H bonds for an overall partial oxidation.〔A. E. Shilov, G. B. Shul’pin, Activation of C–H Bonds by Metal Complexes, ''Chem. Rev.'' 1997, 97(8), 2879–2932. 〕〔A. E. Shilov, G. B. Shul’pin, ''Activation and Catalytic Reactions of Saturated Hydrocarbons in the Presence of Metal Complexes'', Kluwer Academic Publishers, Dordrecht/Boston/London, 2000 (552 p) (Springer, ISBN 978-0-7923-6101-5) http://www.springer.com/chemistry/physical+chemistry/book/978-0-7923-6101-5 〕〔M. Lersch, M. Tilset, Mechanistic Aspects of C-H Activation by Pt Complexes, ''Chem. Rev.''; 2005; 105(6); 2471-2526.〕〔C. I. Herrerias, X. Yao, Z. Li, C.-J. Li, Reactions of C-H Bonds in Water, ''Chem. Rev.''; 2007; 107(6); 2546-2562.〕 == Overview == The Shilov system was discovered by Alexander E. Shilov in 1969-1972 while investigating H/D exchange between isotopologues of CH4 and H2O catalyzed simple transition metal coordination complexes. The Shilov cycle is the partial oxidation of a hydrocarbon to an alcohol or alcohol precursor (RCl) catalyzed by PtIICl2 in an aqueous solution with ()2− acting as the ultimate oxidant. The cycle consists of three major steps, the electrophilic activation of the C-H bond, oxidation of the complex, and the nucleophilic oxidation of the alkane substrate. An equivalent transformation is performed industrially by steam reforming methane to syngas then reducing the carbon monoxide to methanol. The transformation can also performed biologically by methane monooxygenase. Overall Transformation RH + H2O + ()2− → ROH + 2H+ + PtCl2 + 4Cl− 抄文引用元・出典: フリー百科事典『 ウィキペディア（Wikipedia）』 ■ウィキペディアで「Shilov system」の詳細全文を読む スポンサード リンク
|