New Applications of Molybdenum (VI) Catalyzed Oxygen Atom Transfer Reactions PDF Download
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Author: Theo Adrian Hooper Rusmore
Publisher:
ISBN:
Category : Catalysis
Languages : en
Pages : 0
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Author: Theo Adrian Hooper Rusmore
Publisher:
ISBN:
Category : Catalysis
Languages : en
Pages : 0
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Author: Xiaopeng Shan
Publisher:
ISBN:
Category :
Languages : en
Pages : 424
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Book Description
The investigation of oxygen atom transfer (OAT) catalyzed by transition metal complexes continues to provide chemical insight for advanced studies in bioinorganic chemistry as well as industrial applications. Unlike molybdenum(IV/VI) pairs, which received intensive interest from inorganic and bioinorganic chemists for decades, rhenium(V/VII), forming the redox loop involving two-electron or one-oxygen atom processes has only received limited attention. A family of oxorhenium(V) complexes was synthesized from methyltrioxorhenium(VII), abbreviated as MTO, that can be reduced by phosphanes, thiols or sulfides and coordinated by suitable ligands including thiolates, phosphanes, pyridines, phenolates, carboxylates and etc. An unexpected methyl transfer from rhenium to thiolate sulfur was discovered when MTO react with 1,2-ethanedithiol without the presence of a reducing reagent. Ligand displacement was found to be an essential step in OAT reactions catalyzed by rhenium(V) complexes. This allows the oxidant to access rhenium(V) and be activated by the metal subsequently. Kinetic studies of ligand exchange of MeReO(dithiolate)Py with Py or phosphanes and ReO([kappa]2-edt)([kappa]2-edtMe) with phosphanes all revealed in unique correlation behavior when series of substituted ligands were employed. Detailed investigation led us to conclude that a three-step mechanism was involved and caused this unique phenomenon. Further study of the OAT catalytic cycle led us to investigate the geometric effect on the oxidation of rhenium(V) complexes with pyridine N-oxides. Five and six coordinated rhenium(V) complexes with tridentate ligands display an entirely different rate law. The reactions of six-coordinate compounds shows first-order dependence on the concentration of water instead of pyridine N-oxide in the rate law of the reactions of five coordinated rhenium(V) compounds. Steric demand may play the key role in this difference. A catalytic OAT cycle with pyridine N-oxides and sulfide catalyzed by MeReO(PA)2, where PAH is 2-piclinic acid, was investigated. Mechanistic and isotope labeling studies were applied to trap the intermediate, from which a structure was postulated.
Author: Robert Bakhtchadjian
Publisher: Bentham Science Publishers
ISBN: 9815050931
Category : Science
Languages : en
Pages : 137
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This book introduces readers to the fundamentals of oxygen atom transfer reactions. It also gives mechanistic insights into the redox processes occurring through the oxygen atom transfer reactions. It also includes information about catalytic activation of oxygen through enzymes and oxo-metallic complexes. All topics are explored in separate chapters. Key features: - reviews the basic mechanisms in redox processes involving oxo-atom transfer reactions. - presents progress in the biomimetic activation of dioxygen related to the catalytic oxidations by synthetic metal organic complexes. - covers an important class of metal-organic compounds - nickel-oxygen species - generated in catalytic oxidation processes as oxygen atom transfer agents. - explains the mechanistic aspects of the heterogeneous photochemical redox processes via oxo-atom transfer reactions - provides references for further reading It is a reference for both professional scientists in the fields of chemistry, biology and applied sciences, and for graduate and undergraduate students interested in understanding reaction mechanisms involving oxygen.
Author: Edgar Wall Harlan
Publisher:
ISBN:
Category : Ligands
Languages : en
Pages : 354
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Author: Ying Wang
Publisher:
ISBN:
Category :
Languages : en
Pages : 230
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In the case of oxygen atom transfer reaction between tert-butyl hydroperoxide and sulfide catalyzed by Re(V) dithiolato compounds, an induction period is observed due to the slow ligand exchange step. Reaction schemes are proposed to interpret the kinetic data. In both cases, the active intermediates are Re(VII) dioxo species, which were detected at the low temperature. Organic disulfides with both alkyl and aryl substituents are oxidized by hydrogen peroxide when CH3ReO33 (MTO) is used as a catalyst. Thiosulfinate is formed in the first step about an hour with nearly quantitative yield. Kinetics studies of the first oxidation reaction established that two peroxorhenium compounds are the active forms of the catalyst. Rate constants were obtained and a mechanism was proposed in which the electron-rich sulfur attacks the peroxo oxygen of intermediates.
Author: Joshua Miles Smith
Publisher:
ISBN:
Category : Catalysis
Languages : en
Pages : 207
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Author: Martha Susan Reynolds
Publisher:
ISBN:
Category : Molybdenum compounds
Languages : en
Pages : 360
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Author: Atta-ur-Rahman
Publisher: Bentham Science Publishers
ISBN: 1608054756
Category : Science
Languages : en
Pages : 485
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Book Description
Advances in Organic Synthesis is a book series devoted to the latest advances in synthetic approaches towards challenging structures. It presents comprehensive articles written by eminent authorities on different synthetic approaches to selected target molecules and new methods developed to achieve specific synthetic transformations. Contributions are written by eminent scientists and each volume is edited by an authority in the field. Advances in Organic Synthesis is essential for all organic chemists in the academia and industry who wish to keep abreast of rapid and important developments in the field.
Author: Graeme Hanson
Publisher: Springer
ISBN: 1441911391
Category : Medical
Languages : en
Pages : 427
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Book Description
Metal ions in biology is an ever expanding area in science and medicine involving metal ions in proteins and enzymes, their biosynthesis, catalysis, electron transfer, metal ion trafficking, gene regulation and disease. While X-ray crystallography has provided snapshots of the geometric structures of the active site redox cofactors in these proteins, the application of high resolution EPR spectroscopy in conjunction with quantum chemistry calculations has enabled, in many cases, a detailed understanding of a metalloenzymes mechanism through investigations of the geometric and electronic structure of the resting, enzyme-substrate intermediates and product complexes. This volume, Part II of a two-volume set demonstrates the application of high resolution EPR spectroscopy in determining the geometric and electronic structure of active site metal ion centers in iron sulfur cluster containing metalloproteins, mononuclear molybdenum metalloenzymes, manganese-containing enzymes and novel metalloproteins.
Author: Brian Edward Schultz
Publisher:
ISBN:
Category : Molybdenum enzymes
Languages : en
Pages : 328
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