Dioxygen Insertion Studies Into Platinum and Palladium Alkyl Complexes PDF Download
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Author: Allan Robertson Petersen
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Category :
Languages : en
Pages : 0
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Author: Allan Robertson Petersen
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Category :
Languages : en
Pages : 0
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Author: Margaret Louise Scheuermann
Publisher:
ISBN:
Category : Gold compounds
Languages : en
Pages : 119
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Understanding the reactivity of metal complexes with molecular oxygen will facilitate the development of catalysts that can enable the widespread use of molecular oxygen as an oxidant for organic synthesis. This thesis presents two new classes of reactions between metal complexes and molecular oxygen. Neutral five-coordinate Pt complexes were tested for reactivity in the presence of molecular oxygen. In arene solution, the complexes (t̳B̳u̳̳M̳e̳2̳ nacnac)PtMe3 (1, t̳̳B̳u̳M̳e̳2̳ nacnac- = [((4-tBu-2,6-Me2C6H2)NC(CH3))2CH]-), (M̳e̳3̳ Me-nacnac)PtMe3 (2, M̳e̳3̳ Me-nacnac- = [((2,4,6-Me3C6H2)NC(CH3))2CCH3]-), and (t̳B̳u̳2̳ PyPyr)PtMe3 (3, t̳B̳u̳2̳ PyPyr- = 3,5-di-tert-butyl-2-(2-pyridyl)pyrrolide) reacted immediately with oxygen to form peroxo species in which two oxygen atoms bridge between the metal center and a carbon atom in the ligand backbone. In contrast, no reaction between ( i̳P̳r̳2̳ AnIm)PtMe3 (4a, i̳P̳r̳2̳ AnIm− = [o- C66H4-{N(C6H3 i Pr2)}(CH=NC6H3 i Pr2)]−) or (M̳e̳3̳ AnIm)PtMe3 (4b, M̳e̳̳3̳ AnIm− = [o-C6H4- {N(C6H2Me3)}(CH=NC6H2Me3)]−) and oxygen was observed. As activation of oxygen by five- coordinate PtIV species was found to involve cooperation between the metal center and the ligand, the ability of the ligand to participate in the oxygen binding appears to be a vital component. Oxygen atom transfer reactions of the novel peroxo species are also presented. In a separate study, an unusual reaction involving the activation of both molecular oxygen and a C-H bond at the same metal center was investigated. Pd(P(Ar)(tBu)2)2 (15, Ar = naphthyl) was found to react with molecular oxygen at room temperature in arene solvent to form a hydroxide dimer in which one equivalent of phosphine per Pd was lost and the remaining phosphine was cyclometalated through the naphthyl ring. At low temperature, two intermediates were observed. The nature of these intermediates suggests a mechanism involving initial reaction of Pd(P(Ar) (tBu)2)2 with O2 followed by the C-H activation step. In a final chapter unrelated to oxygen reactivity, the generation and characterization of a gold III̳-alkene complex by NMR and X-ray crystallography is presented. Such species have been proposed as intermediates in catalytic reactions but until recently none had been observed.
Author: Allan J. Canty
Publisher: Springer
ISBN: 3642174299
Category : Science
Languages : en
Pages : 195
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Kyle A. Grice, Margaret L. Scheuermann and Karen I. Goldberg: Five-Coordinate Platinum(IV) Complexes.- Jay A. Labinger and John E. Bercaw: The Role of Higher Oxidation State Species in Platinum-Mediated C-H Bond Activation and Functionalization.- Joy M. Racowski and Melanie S. Sanford: Carbon-Heteroatom Bond-Forming Reductive Elimination from Palladium(IV) Complexes.- Helena C. Malinakova: Palladium(IV) Complexes as Intermediates in Catalytic and Stoichiometric Cascade Sequences Providing Complex Carbocycles and Heterocycles.- Allan J. Canty and Manab Sharma: h1-Alkynyl Chemistry for the Higher Oxidation States of Palladium and Platinum.- David C. Powers and Tobias Ritter: Palladium(III) in Synthesis and Catalysis.- Marc-Etienne Moret: Organometallic Platinum(II) and Palladium(II) Complexes as Donor Ligands for Lewis-Acidic d10 and s2 Centers.
Author: P. Henry
Publisher: Springer Science & Business Media
ISBN: 940099446X
Category : Science
Languages : en
Pages : 449
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The field of organometallic chemistry has emerged over the last twenty-five years or so to become one of the most important areas of chemistry, and there are no signs of abatement in the intense current interest in the subject, particularly in terms of its proven and potential application in catalytic reactions involving hydrocarbons. The development of the organometallic/ catalysis area has resulted in no small way from many contributions from researchers investigating palladium systems. Even to the well-initiated, there seems a bewildering and diverse variety of organic reactions that are promoted by palladium(II) salts and complexes. Such homogeneous reactions include oxidative and nonoxidative coupling of substrates such as olefins, dienes, acetylenes, and aromatics; and various isomerization, disproportionation, hydrogenation, dehydrogenation, car bonylation and decarbonylation reactions, as well as reactions involving formation of bonds between carbon and halogen, nitrogen, sulfur, and silicon. The books by Peter M. Maitlis - The Organic Chemistry of Palladium, Volumes I, II, Academic Press, 1971 - serve to classify and identify the wide variety of reactions, and access to the vast literature is available through these volumes and more recent reviews, including those of J. Tsuji [Accounts Chem. Res. , 6, 8 (1973); Adv. in Organometal. , 17, 141 (1979)], R. F. Heck [Adv. in Catat. , 26, 323 (1977)], and ones by Henry [Accounts Chem. Res. , 6, 16 (1973); Adv. in Organometal. , 13, 363 (1975)]. F. R. Hartley's book - The Chemistry of Platinum and Palladium, App!. Sci. Pub!.
Author:
Publisher:
ISBN:
Category :
Languages : en
Pages :
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Author: Iwao Omae
Publisher: Springer Science & Business Media
ISBN: 4431546049
Category : Science
Languages : en
Pages : 214
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This book provides a review of cyclometalation reactions and organometallic intramolecular-coordination five-membered ring products, the most active type of reactions in synthetic organic reactions and their products. Included is the discovery of intramolecular-coordination bonds in cyclometalation reactions and the characteristics of those reactions, as well as the reasons that their five-membered ring compounds are very easily synthesized through such reactions. In addition, the applications of cyclometalation reactions and five-membered ring products, synthetic applications, catalysts, and other products are described. These topics are of special interest for industrial researchers.
Author:
Publisher:
ISBN:
Category : Chemistry
Languages : en
Pages : 2540
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Author: Gerard van Koten
Publisher: Springer
ISBN: 3642310818
Category : Science
Languages : en
Pages : 363
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Gerard van Koten: The Mono-anionic ECE-Pincer Ligand - a Versatile Privileged Ligand Platform: General Considerations.- Elena Poverenov, David Milstein: Non-Innocent Behavior of PCP and PCN Pincer Ligands of Late Metal Complexes.- Dean M. Roddick: Tuning of PCP Pincer Ligand Electronic and Steric Properties.- Gemma R. Freeman, J. A. Gareth Williams: Metal Complexes of Pincer Ligands: Excited States, Photochemistry, and Luminescence.- Davit Zargarian, Annie Castonguay, Denis M. Spasyuk: ECE-Type Pincer Complexes of Nickel.- Roman Jambor and Libor Dostál: The Chemistry of Pincer Complexes of 13 - 15 Main Group Elements.- Kálmán J. Szabo: Pincer Complexes as Catalysts in Organic Chemistry.- Jun-ichi Ito and Hisao Nishiyama: Optically Active Bis(oxazolinyl)phenyl Metal Complexes as Multi-potent Catalysts.- Anthony St. John, Karen I. Goldberg, and D. Michael Heinekey: Pincer Complexes as Catalysts for Amine Borane Dehydrogenation.- Dmitri Gelman and Ronit Romm: PC(sp3)P Transition Metal Pincer Complexes: Properties and Catalytic Applications.- Jennifer Hawk and Steve Craig: Physical Applications of Pincer Complexes.
Author: Richard J. Puddephatt
Publisher: Elsevier
ISBN: 9780080423166
Category : Organometallic chemistry
Languages : en
Pages : 670
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Author: Jerold Howard Price
Publisher:
ISBN:
Category :
Languages : en
Pages : 344
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