Prediction of 195Pt NMR Chemical Shifts by Density Functional用密度泛函预测195Pt NMR化学位移.pptVIP

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2017-03-08 发布于上海
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Prediction of 195Pt NMR Chemical Shifts by Density Functional用密度泛函预测195Pt NMR化学位移.ppt

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Prediction of 195Pt NMR Chemical Shifts by Density Functional用密度泛函预测195Pt NMR化学位移

* * Density Functional Theory Examination of the C-H Activation Step of the Catalytica Methane Activation Reaction: Pyrimidine Ligand Protonation, Chloridevs. Bisulfate ligands, and Metathesis vs. Oxidative Addition Thomas M. Gilbert1 and Tom Ziegler Department of Chemistry, University of Calgary 2500 University Drive NW, Calgary, Alberta, Canada T2N 1N4 1 On sabbatical from Department of Chemistry and Biochemistry, Northern Illinois University, Dekalb, Illinois, USA 60115 Introduction It has proven difficult to derivatize methane specifically and in high yield. Recent work has focussed on sulfonating methane with fuming sulfuric acid. This is motivated by the facts that: one, the presence of the highly oxidized sulfonate group lessens the chance of further oxidation at carbon; two, the ready hydrolysis of the sulfonate group provides the useful commodity chemical, methanol; and three, the SO2 by-product readily oxidizes to SO3, providing a plausible catalytic cycle. In this regard, the recent report from Periana and coworkers at Catalytica provides great promise. They found that methane reacts with fuming sulfuric acid solvent in the presence of (bipyrimidine)PtCl2 to give only methyl bisulfate, with no products of oxidation or further substitution. Remarkably, the catalyst shows impressive stability at the required reaction temperatures of 180 °C. Even more remarkably, yields of methanol via methyl bisulfate in excess of 70% have been obtained. R. A. Periana, D. J. Taube, S. Gamble, H. Taube, T. Satoh, H. Fujii Science 1998, 280, 560 - 564 The Catalytica Methane-to-Methyl Bisulfate Process Periana et al propose the following mechanism based on isotopic labeling studies, the use of other nitrogenous ligands, and the use of Pt (IV) compounds instead of Pt (II) catalysts: A number of computational studies have appeared addressing various aspects of this mechanism. Hush and coworkers compared model energies for several sulfuric-acid-solvated and -free