Synthesis and Reactivity of Aminocyclopentadienyl Ruthenium Complexes PDF Download
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Author: Thomas Evan Vos
Publisher:
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Languages : en
Pages : 510
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Author: Thomas Evan Vos
Publisher:
ISBN:
Category :
Languages : en
Pages : 510
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Author: Shun-Ichi Murahashi
Publisher: John Wiley & Sons
ISBN: 3527605797
Category : Science
Languages : en
Pages : 398
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In this comprehensive book, one of the leading experts, Shun-Ichi Murahashi, presents all the important facets of modern synthetic chemistry using Ruthenium, ranging from hydrogenation to metathesis. In 14 contributions, written by an international authorship, readers will find all the information they need about this fascinating and extraordinary chemistry. The result is a high quality information source and a indispensable reading for everyone working in organometallic chemistry. From the contents: Introduction (S.-I. Murahashi) Hydrogenation and Transfer Hydrogenation (M. Kitamura and R. Noyori) Oxidations (S.-I. Murahashi and N. Komiya) Carbon-Carbon Bond Formations via Ruthenacycle Intermediates (K. Itoh) Carbon-Carbon Bond Formation via pi-Allylruthenium Intermediates (T. Mitsudo) Olefin Metathesis (R. H. Grubbs) Cyclopropanation (H. Nishiyama) Nucleophilic Addition to Alkynes and Reactions via Vinylidene Intermediates (P. Dixneuf) Reactions via C-H Activation (N. Chatani) Lewis Acid Reactions (E. P. Kundig) Reactions with CO and CO2 (T. Mitsudo) Isomerization of Organic Substrates Catalyzed by Ruthenium Complexes (H. Suzuki) Radical Reactions (H. Nagashima) Bond Cleavage Reactions (S. Komiya)
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Languages : en
Pages : 417
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The products and mechanisms of the thermal reactions of several complexes of the general structure (PMe3)4Ru(X)(Y) and (DMPM)2Ru(X)(Y) where X and Y are hydride, aryl, and benzyl groups, have been investigated. The mechanism of decomposition depends critically on the structure of the complex and the medium in which the thermolysis is carried out. The alkyl hydride complexes are do not react with alkane solvent, but undergo C-H activation processes with aromatic solvents by several different mechanisms. Thermolysis of (PMe3)4Ru(Ph)(Me) or (PMe3)4Ru(Ph)2 leads to the ruthenium benzyne complex (PMe3)4Ru([eta]2-C6H4) (1) by a mechanism which involves reversible dissociation of phosphine. In many ways its chemistry is analogous to that of early rather than late organo transition metal complexes. The synthesis, structure, variable temperature NMR spectroscopy and reactivity of ruthenium complexes containing aryloxide or arylamide ligands are reported. These complexes undergo cleavage of a P-C bond in coordinated trimethylphosphine, insertion of CO and CO2 and hydrogenolysis. Mechanistic studies on these reactions are described. The generation of a series of reactive ruthenium complexes of the general formula (PMe3)4Ru(R)(enolate) is reported. Most of these enolates have been shown to bind to the ruthenium center through the oxygen atom. Two of the enolate complexes 8 and 9 exist in equilibrium between the O- and C-bound forms. The reactions of these compounds are reported, including reactions to form oxygen-containing metallacycles. The structure and reactivity of these ruthenium metallacycles is reported, including their thermal chemistry and reactivity toward protic acids, electrophiles, carbon monoxide, hydrogen and trimethylsilane. 243 refs., 10 tabs.
Author: Uwe Theo Bornscheuer
Publisher: John Wiley & Sons
ISBN: 3527607129
Category : Science
Languages : en
Pages : 368
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From reviews to the first edtion: "Bornscheuer and Kazlauskas have set out, and succeeded, in producing a definitive manual on hydrolytic enzymes (especially lipases, esterases, and proteases) for organic chemists. This is quite simply the best book of its type and can be unreservedly recommended to organic chemists who have an interest in using hydrolytic enzymes in synthesis." (Nicholas J. Turner, University of Edinburgh) "The book is an indispensable source of information on the use of hydrolases in organic synthesis. The subject matter is very well set out, and the chapters are clearly written and presented from a critical viewpoint. Bornscheuer and Kazlauskas have succeeded admirably in describing the capabilities and limitations of the use of hydrolytic enzymes and in critically evaluating them. No library should be without the book." (Fritz Theil, WITEGA Angewandte Werkstoff-Forschung GmbH, Berlin) The second edition of this extremely successful and well-proven book presents recent developments in the use of hydrolases for organic synthesis, reflecting in particular the enormous progress made in enzyme discovery and optimization with a new chapter on "Protein Sources and Optimization of Biocatalyst Performance". The renowned authors survey the stereoselective reactions of hydrolases, especially lipases, esterases and proteases, giving researchers an overview of what has worked in the past so that they can judge how to solve their own synthetic problems. In total, the book contains over one thousand chemical structures, rounded off by some 1,800 invaluable references.
Author: Yijing Xu
Publisher:
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Category :
Languages : en
Pages :
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Author: Richard Ira Michelman
Publisher:
ISBN:
Category :
Languages : en
Pages : 344
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Author: Tse-Lok Ho
Publisher: John Wiley & Sons
ISBN: 0471682438
Category : Science
Languages : en
Pages : 550
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From reviews of previous volumes: "Essential for chemistry collections at the university and research levels." --New York Public Library "Highly recommended...lots of succinct, practical information on recent developments...in a format that is easy to use. The reagents are taken up in alphabetical order (common usage names, not CAS indexing code names), sometimes several to a page, sometimes several pages to a reagent. One can expect to find how to make the reagent (in loose terms), or where it can be bought, what it is good for, and where to seek complete details. As with previous volumes, one can profit from just browsing, even if one does not feel a need to look up any particular subject. It is thus a secondary function of the book to help one keep abreast of the field, and it would be a rare chemist who would not learn something new and useful from a casual perusal of the pages." --Journal of the American Chemical Society REAGENTS FOR ORGANIC SYNTHESIS Volume 1 1967 (0-471-25875-X) 1,475 pp. Volume 2 1969 (0-471-25876-8) 538 pp. Volume 3 1972 (0-471-25879-2) 401 pp. Volume 4 1974 (0-471-25881-4) 660 pp. Volume 5 1975 (0-471-25882-2) 864 pp. Volume 6 1977 (0-471-25873-3) 765 pp. Volume 7 1979 (0-471-02918-1) 487 pp. Volume 8 1980 (0-471-04834-8) 602 pp. Volume 9 1981 (0-471-05631-6) 596 pp. Volume 10 1982 (0-471-86636-9) 528 pp. Volume 11 1984 (0-471-88628-9) 669 pp. Volume 12 1986 (0-471-83469-6) 643 pp. Volume 13 1988 (0-471-63007-1) 472 pp. Volume 14 1989 (0-471-50400-9) 386 pp. Volume 15 1990 (0-471-52113-2) 432 pp. Volume 16 1992 (0-471-52721-1) 435 pp. Volume 17 1994 (0-471-00074-4) 464 pp. Volume 18 1999 (0-471-24477-5) 518 pp. Volume 19 1999 (0-471-32709-3) 504 pp. Volume 20 2000 (0-471-36999-3) 552 pp. Volume 21 2002 (0-471-21393-4) 608 pp. Volume 22 2006 (0-471-68243-8) 504 pp.
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Several ruthenium complexes with non-dative heteroatomic ligands were prepared and fully characterized, including TpRu(PMe3)2X (X = OH, OPh, OMe, SH; Tp = hydridotris(pyrazolyl)borate). At elevated temperatures (90 °C -- 130 °C), complexes of the type TpRu(PMe3)2X (X = OH, OPh, Me, Ph or NHPh) undergo regioselective HD exchange with deuterated arenes. In addition, for X = OH or NHPh, HD exchange occurs at hydroxo and anilido ligands, respectively. For X = OH, OPh, Me, Ph or NHPh, isotopic exchange occurs at the Tp 4-positions with only minimal deuterium incorporation at the Tp 3- or 5-positions. TpRu(PMe3)2Cl, TpRu(PMe3)2OTf (OTf = trifluoromethanesulfonate) and TpRu(PMe3)2SH do not initiate HD exchange in C6D6 after extended periods of time at elevated temperatures. Mechanistic studies indicate that the likely pathway for the HD exchange involves ligand dissociation (PMe3 or NCMe), Ru-mediated activation of an aromatic C-D bond, and deuteration of basic heteroatomic ligand (hydroxo or anilido) or Tp positions via intermolecular D+ transfer. The Ru(II) complexes TpRu(PMe3)2OR (R = H or Ph) react with excess phenylacetylene at elevated temperatures to produce the phenylacetylide complex TpRu(PMe3)2(CðCPh). Kinetic studies indicate that the reaction of TpRu(PMe3)2OH and phenylacetylene likely proceeds through a pathway that involves TpRu(PMe3)2OTf as a catalyst. The reaction of TpRu(PMe3)2OH with 1,4-cyclohexadiene at elevated temperature forms benzene and TpRu(PMe3)2H, while TpRu(PMe3)2OPh does not react with 1,4-cyclohexadiene even after 20 days at 85 °C. The paramagnetic Ru(III) complex [TpRu(PMe3)2OH][OTf] is formed upon single-electron oxidation of TpRu(PMe3)2OH with AgOTf. Reactivity studies suggest that [TpRu(PMe3)2OH][OTf] initiates reactions, including hydrogen atom abstraction, with C-H bonds that have bond dissociation energy d"82 kcalD ol. Experimentally, the O-H bond strength of the Ru(II).
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Ru carbene complexes have been investigated for potential application toward carbon-nitrogen bond forming and breaking reactions. The reactivity of Grubbs-type olefin metathesis catalysts (Cl)2(L)(L')Ru=CHPh (L = L' = PCy3 or PPh3; L = PCy3 and L' = H2MesNHC) has been studied with cyclic and acyclic imines. The Ru benzylidene complex (Cl)2(PCy3)2Ru=CHPh undergoes a ligand exchange reaction with 1-pyrroline at room temperature, and oligomerizes 1-pyrroline at 90 oC. The low molecular weight poly(1-pyrroline) has been isolated and characterized. The Ru benzylidene complex has no reactivity toward acyclic imine C=N bonds, but reacts with enamine C=C bonds that form through tautomerization of imines. The Ru amido complexes, (PCP)Ru(CO)(NHPh) and (PCP)Ru(CO)(NHPh)(PMe3) (PCP = 2,6-(CH2P-t-Bu2)C6H3), have been synthesized and characterized. Reaction of (PCP)Ru(CO)(NHPh)(PMe3) with acetonitrile produces the amidinate complex (PCP)Ru(CO)(NHC(Me)NPh). Kinetic studies have demonstrated the formation of the amidinate complex occurs through dissociation of the PMe3 ligand, coordination of MeCN, and intramolecular nucleophilic attack of the amido ligand toward MeCN. The intramolecular nucleophilic attack reaction has been extensively studied with aromatic nitriles, carbodiimides, isocyanates, carboxamides and aldehydes. Reaction of (PCP)Ru(CO)(NHC(Me)NPh) with pentafluorobenzonitrile results in formation of a new amidinate complex (PCP)Ru(CO)(NHC(C6F5)NPh). The complex (PCP)Ru(CO)(NHC(C6F5)NPh) can initiate a C-F bond cleavage reaction of C6F5CN with ortho regioselectivity in the presence of ROH (R = H or Me). Reaction of five-coordinate complex (PCP)Ru(CO)(OTf) (OTf = OSO2CF3) with NaBAr'4 (Ar' = 3,5-(CF3)2C6H3) under different conditions results in formation of [(PCP)Ru(CO)(ClCH2Cl)][BAr'4], [(PCP)Ru(CO)(N2)][BAr'4] or [(PCP)Ru(CO)(FC6H5)][BAr'4]. Calculations have confirmed that the possible four-coordinate Ru complex with double agostic interactions has a higher ground state.
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