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Transition Metal Complexes Bearing Hemilabile Pincer Ligands
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Book Synopsis Transition Metal Complexes Bearing Hemilabile Pincer Ligands by : Ashwin Gopalan Nair
Download or read book Transition Metal Complexes Bearing Hemilabile Pincer Ligands written by Ashwin Gopalan Nair and published by . This book was released on 2017 with total page 381 pages. Available in PDF, EPUB and Kindle. Book excerpt: This thesis describes the synthesis of new Ag(I), Ru(II), Ni(II), Au(I) and Au(III) complexes containing an imidazolyl-pyrazolyl ligand motif (NCNMe- methylene linker, and NCNEt- ethylene linker). The synthesised complexes were tested as catalysts for a number of organic transformations.
Book Synopsis The Chemistry of Pincer Compounds by : David Morales-Morales
Download or read book The Chemistry of Pincer Compounds written by David Morales-Morales and published by Elsevier. This book was released on 2011-08-11 with total page 467 pages. Available in PDF, EPUB and Kindle. Book excerpt: Pincer complexes are formed by the binding of a chemical structure to a metal atom with at least one carbon-metal bond. Usually the metal atom has three bonds to a chemical backbone, enclosing the atom like a pincer. The resulting structure protects the metal atom and gives it unique properties.The last decade has witnessed the continuous growth in the development of pincer complexes. These species have passed from being curiosity compounds to chemical chameleons able to perform a wide variety of applications. Their unique metal bound structures provide some of the most active catalysts yet known for organic transformations involving the activation of bonds. The Chemistry of Pincer Compounds details use of pincer compounds including homogeneous catalysis, enantioselective organic transformations, the activation of strong bonds, the biological importance of pincer compounds as potential therapeutic or pharmaceutical agents, dendrimeric and supported materials. * Describes the chemistry and applications of this important class of organometallic and coordination compounds* Covers the areas in which pincer complexes have had an impact* Includes information on more recent and interesting pincer compounds not just those that are well-known
Book Synopsis Transition Metal Complexes of Neutral Eta1-Carbon Ligands by : Remi Chauvin
Download or read book Transition Metal Complexes of Neutral Eta1-Carbon Ligands written by Remi Chauvin and published by Springer Science & Business Media. This book was released on 2010-01-12 with total page 260 pages. Available in PDF, EPUB and Kindle. Book excerpt: This book is part of a series that gives the broad scientific readership a comprehensive summary and critical overview of specific topics in the field of organometallic chemistry. This text focuses on transition metal complexes of neutral eta1-carbon ligands.
Book Synopsis Late Transition Metal Complexes of Pentafluorophenylphosphino-pincer Ligands by : Bradley George Anderson
Download or read book Late Transition Metal Complexes of Pentafluorophenylphosphino-pincer Ligands written by Bradley George Anderson and published by . This book was released on 2012 with total page 376 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Book Synopsis Metal-Ligand Multiple Bonds by : William A. Nugent
Download or read book Metal-Ligand Multiple Bonds written by William A. Nugent and published by Wiley-Interscience. This book was released on 1988-11-14 with total page 360 pages. Available in PDF, EPUB and Kindle. Book excerpt: The only comprehensive one-volume text/reference on metal-ligand multiple bonds. Stresses the unified nature of the field and includes handy new tabulations of data. The flow within each subtopic is oxygen to nitrogen to carbon. Coverage is up-to-date--virtually every subtopic leads to interesting questions for future research. Presents information otherwise scattered through hundreds of publications.
Book Synopsis Transition Metal Complexes with P,N-Ligands and Silylenes: Synthesis and Catalytic Studies by : Eva Neumann
Download or read book Transition Metal Complexes with P,N-Ligands and Silylenes: Synthesis and Catalytic Studies written by Eva Neumann and published by Cuvillier Verlag. This book was released on 2006-02-15 with total page 244 pages. Available in PDF, EPUB and Kindle. Book excerpt: The term ligand [latin, ligare = bind] has its origin in coordination chemistry. It denotes a molecule that is able to bind to a metal center in most cases via one or several free electron pairs.[1] Ligands can be described by the number of electron-pair donor atoms as monodentate, bidentate, tridentate etc. ligands. The latter are also called chelating ligands [greek, chele = (crab’s) claw]. A typical classification of ligands is according to their electronic properties. They serve either as a σ-donating, σ-donating/π-accepting, or σ,π-donating/π-accepting ligands.[2] A more practical, often encountered approach is the classification of ligands according to their donor atoms, especially when larger molecules and molecules containing heteroatoms are regarded (compare 1.2). Coordination chemistry was already established in the 19th century. In 1893 Alfred Werner suggested an octahedral arrangement of ligands coordinated to a central metal ion for many compounds. This explained, for example, the appearance and reactivity of four different cobalt(III) complexes (Figure 1.1), when CoCl2 is dissolved in aqueous ammonia and then oxidized by air to the +3 oxidation state. The formulas of these complexes can be written as depicted in Figure 1.1. Werner’s work was rewarded with the Nobel prize in 1913.[3]
Book Synopsis Pincer Compounds by : David Morales-Morales
Download or read book Pincer Compounds written by David Morales-Morales and published by Elsevier. This book was released on 2018-04-11 with total page 756 pages. Available in PDF, EPUB and Kindle. Book excerpt: Pincer Compounds: Chemistry and Applications offers valuable state-of-the-art coverage highlighting highly active areas of research—from mechanistic work to synthesis and characterization. The book focuses on small molecule activation chemistry (particularly H2 and hydrogenation), earth abundant metals (such as Fe), actinides, carbene-pincers, chiral catalysis, and alternative solvent usage. The book covers the current state of the field, featuring chapters from renowned contributors, covering four continents and ranging from still-active pioneers to new names emerging as creative strong contributors to this fascinating and promising area. Over a decade since the publication of Morales-Morales and Jensen’s The Chemistry of Pincer Compounds (Elsevier 2007), research in this unique area has flourished, finding a plethora of applications in almost every single branch of chemistry—from their traditional application as very robust and active catalysts all the way to potential biological and pharmaceutical applications. Describes the chemistry and applications of this important class of organometallic and coordination compounds Includes contributions from global leaders in the field, featuring pioneers in the area as well as emerging experts conducting exciting research on pincer complexes Highlights areas of promising and active research, including small molecule activation, earth abundant metals, and actinide chemistry
Book Synopsis Transition metal complexes bearing soft anionic ligands by : Stuart Taylor Schwab
Download or read book Transition metal complexes bearing soft anionic ligands written by Stuart Taylor Schwab and published by . This book was released on 1986 with total page 254 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Book Synopsis Transition Metal Complexes of Cyclic Polyolefins by : G. Deganello
Download or read book Transition Metal Complexes of Cyclic Polyolefins written by G. Deganello and published by . This book was released on 1979 with total page 496 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Book Synopsis Synthesis of Transition Metal Complexes Supported by Mixed Donor PSiP' Bis-Phosphino Silyl Pincer Ligands by : Marshall Hoey
Download or read book Synthesis of Transition Metal Complexes Supported by Mixed Donor PSiP' Bis-Phosphino Silyl Pincer Ligands written by Marshall Hoey and published by . This book was released on 2016 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt:
Book Synopsis Studies in Tridentate Hemilabile Ligands and Their Metal Complexes by : Kathryn Harkup
Download or read book Studies in Tridentate Hemilabile Ligands and Their Metal Complexes written by Kathryn Harkup and published by . This book was released on 2004 with total page 406 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Book Synopsis Syntheses and Reactivity Studies of Transition Metal Complexes Featuring Metal - Main Group Multiple Bonds by : Meg E. Fasulo
Download or read book Syntheses and Reactivity Studies of Transition Metal Complexes Featuring Metal - Main Group Multiple Bonds written by Meg E. Fasulo and published by . This book was released on 2012 with total page 120 pages. Available in PDF, EPUB and Kindle. Book excerpt: The ruthenium triflate complex Cp*(PiPr3)RuOTf (1) was generated from the reaction of Cp*(PiPr3)RuCl with Me3SiOTf in dibutyl ether. Complex 1 reacted with primary and secondary silanes to produce a family of Ru(IV) silyl dihydride complexes of the type Cp*(PiPr3)Ru(H)2(SiRR'OTf) (3 - 12). Structural analyses of complexes 8 (R = R' = Ph) and 12 (R = R' = fluorenyl) revealed the presence of a tetrahedral silicon center and a four-legged piano stool geometry about ruthenium. Anion abstraction from Cp*(PiPr3)Ru(H)2(SiHROTf) by [Et3Si*toluene][B(C6F5)4] afforded hydrogen-substituted cationic ruthenium silylene complexes [Cp*(PiPr3)Ru(H)2(=SiHR)][B(C6F5)4] (R = Mes (13), R = Si(SiMe3) (14)) that display a significant Ru - H ... Si interaction, as indicated by relatively large 2JSiH coupling constants (2JSiH = 58.2 Hz (13), 2JSiH = 37.1 Hz (14)). The syntheses of secondary silylene complexes [Cp*(PiPr3)Ru(H)2(=SiRR')][B(C6F5)4] (R = R' = Ph (15); R = Ph, R' = Me (16), R = R' = fluorenyl (17)) were also achieved by anion abstraction with [Et3Si*toluene][B(C6F5)4]. Complexes 15 - 17 do not display strong Ru - H ... Si secondary interactions, as indicated by very small 2JSiH coupling constant values. The cationic ruthenium silylene complex [Cp*(PiPr3)Ru(H)2(SiHMes)] [CB11H6Br6], a catalyst for olefin hydrosilations with primary silanes, was isolated and characterized by X-ray crystallography. Relatively strong interactions between the silylene Si atom and Ru-H hydride ligands appear to reflect a highly electrophilic silicon center. Kinetic and mechanistic studies on hydrosilations with this catalyst reveal a fast, initial addition of the Si-H bond of the silylene complex to the olefin. Subsequent migration of a hydride ligand to silicon produces a 16-electron intermediate, which can be trapped by olefin, resulting in inhibition of catalysis, or intercepted by the silane substrate. The latter reaction pathway, involving oxidative addition of the Si-H bond and a somewhat concomitant loss of product, is the rate-determining step in the catalytic cycle. Reactions of the cationic ruthenium silylene complexes [Cp*(PiPr3)Ru(H)2(=SiRR')][B(C6F5)4] (R = Mes, R' = H, 1; R = R' =Ph, 2) with alkenes, alkynes, ketones, and Lewis bases were explored. Addition of 1-hexene, 3,3-dimethylbut-1-ene, styrene, and cyclopentene to 1 afforded the disubstituted silylene products [Cp*(PiPr3)Ru(H)2(=SiMesR)][B(C6F5)4] (R = Hex, 3; R = CH2CH2tBu, 4; R = CH2CH2Ph, 5; R = C5H9, 6). Analogous reactions with 2-butyne and 3,3-dimethylbut-1-yne yielded the vinyl-substituted silylene complexes [Cp*(PiPr3)Ru(H)2(=Si(CR=CHR')Mes)][B(C6F)4] (R = R' = Me, 7; R = H, R' = tBu, 8). Complex 1 undergoes reactions with ketones to give the heteroatom-substituted silylene complexes [Cp*(PiPr3)Ru(H)2(=Si(OCHPhR)Mes)][B(C6F)4] (R = Ph, 9; R = Me, 10). Interestingly, complexes 3 - 8 display a weak interaction between the hydride ligands and the silicon center, while 9 and 10 exhibit a relatively large interaction (as determined by 2JSiH values). The reaction of isocyanates with 1 resulted in the silyl complexes [Cp*(PiPr3)Ru(H)2(Si(Mes)[n2-O(CH)(NC6H4R)][B(C6F5)4] (R = H, 11; R = CF3, 12), and an intermediate in this transformation is observed. Complex 2 was subjected to various Lewis bases to yield the base-stabilized silylene complexes [Cp*(PiPr3)Ru(H)2(SiPh2*L)][B(C6F)4] (L = DMAP, 13; L = Ph2CO, 14; L = PhCONH2, 15; L = NHMePh, 16, L = tBuSONH2, 18) and the reaction of 1 with NHMePh gave [Cp*(PiPr3)Ru(H)2(SiHMes*NHMePh)][B(C6F)4]. The cationic germylene complex [Cp*(PiPr3)Ru(H)2(=GeMes2)][OTf] (1) was synthesized from the reaction of Cp*(PiPr3)RuOTf with H2GeMes2, and addition of DMAP to 1 yielded the neutral germylene complex [Cp*(PiPr3)Ru(H)(=GeMes2) (2). The reaction of H3GeTrip and Cp*(PiPr3)RuCl gave the germyl complex Cp*(PiPr3)Ru(H)2(GeHTripCl) (3), which undergoes a reaction with Li(Et2O)2[B(C6F5)4] to afford the cationic H-substituted germylene complex [Cp*(PiPr3)Ru(H)2(=GeHTrip)][B(C6F5)4] (4). Addition of 1-hexene, 3,3-dimethylbut-1-ene, styrene, and allyl chloride to 4 afforded the disubstituted germylene products [Cp*(PiPr3)Ru(H)2(=GeTripR)][B(C6F5)4] (R = Hex, 5; R = CH2CH2Ph, 6; R = CH2CH2tBu, 7; R = CH2CH2CH2Cl, 8). Analogous reactions with 2-butyne and 3,3-dimethylbut-1-yne yielded the vinyl-substituted germylene complexes [Cp*(PiPr3)Ru(H)2(=Ge(CR=CHR')Trip)][B(C6F)4] (R = H, R' = tBu, 9; R = R' = Me, 10). New di(phosphine)-supported rhodium and iridium silyl complexes were synthesized. Reactions of the di(t-butylphosphino)ethane complex (dtbpe)Rh(CH2Ph) with Ph2SiH2 and Et2SiH2 resulted in isolation of (dtbpe)Rh(H)2(SiBnPh2) (1, Bn = CH2Ph) and (dtbpe)Rh(H)2(SiBnEt2) (2), respectively. Both 1 and 2 display strong interactions between the rhodium hydride ligands and the silyl ligand, as indicated by large 2JSiH values (44.4 and 52.1 Hz). The reaction of (dtbpm)Rh(CH2Ph) (dtbpm = di(t-butylphosphino)methane) with Mes2SiH2 gave the pseudo-three-coordinate Rh complex (dtbpm)Rh(SiHMes2) (3), which is stabilized in the solid state by agostic interactions between the rhodium center and two C - H bonds of a methyl substituent of a mesityl group. The analogous germanium compound (dtbpm)Rh(GeHMes2) (4) is also accessible. Complex 3 readily undergoes reactions with diphenylacetylene, phenylacetylene, and 2-butyne to give the silaallyl complexes (dtbpm)Rh[Si(CPh=CHPh)Mes2] (5), (dtbpm)Rh[Si(CH=CHPh)Mes2] (7), and (dtbpm)Rh(Si(CMe=CHMe)Mes2) (8) via net insertions into the Si - H bond. The germaallyl complexes (dtbpm)Rh[Ge(CPh=CHPh)Mes2] (6) and (dtbpm)Rh[Ge(CMe=CHMe)Mes2] (9) were synthesized under identical conditions starting from 4. The reaction of (dtbpm)Rh(CH2Ph) with 1 equiv of TripPhSiH2 yielded (dtbpm)Rh(H)2[5,7-diisopropyl-3-methyl-1-phenyl-2,3-dihydro-1H-silaindenyl-kSi] (11), and catalytic investigations indicate that both (dtbpm)Rh(CH2Ph) and 11 are competent catalysts for the conversion of TripPhSiH2 to 5,7-diisopropyl-3-methyl-1-phenyl-2,3-dihydro-1H-silaindole. A dtbpm-supported Ir complex, [(dtbpm)IrCl]€2, was used to access the dinuclear bridging silylene complexes [(dtbpm)IrH](SiPh2)(Cl)2[(dtbpm)IrH] (12) and [(dtbpm)IrH](SiMesCl)( -Cl)(H)[(dtbpm)IrH] (13). The reaction of [(dtbpm)IrCl]2 with a sterically bulky primary silane, (dmp)SiH3 (dmp = 2,6-dimesitylphenyl), allowed isolation of the mononuclear complex (dtbpm)Ir(H)4(10-chloro-1-mesityl-5,7-dimethyl-9,10-dihydrosilaphenanthrene-Si) (14), in which the dmp substituent has undergone C-H activation. The dichloride complex Cp*(Am)WCl2 (1, Am = [(iPrN)2CMe]- ) reacted with the primary silanes PhSiH3, (p-tolyl)SiH3, (3,5-xylyl)SiH3, and (C6F5)SiH3 to produce the W(VI) (silyl)trihydrides Cp*(Am)W(H)3(SiHPhCl) (2), Cp*(Am)W(H)3(SiHTolylCl) (3), Cp*(Am)W(H)3(SiHXylylCl) (4), and Cp*(Am)W(H)3[SiH(C6F5)Cl] (5). In an analogous manner, 1 reacted with PhSiH2Cl to give Cp*(Am)W(H)3(SiPhCl2) (6). Complex 6 can alternatively be quantitatively produced from the reaction of 2 with Ph3CCl. NMR spectroscopic studies and X-ray crystallography reveal an interligand H ... Si interaction between one W - H and the chlorosilyl group, which is further supported by DFT calculations. Complexes of Ru(II) containing the pincer ligand [-N(2-PPh2-4-Me-C6H3)2] (PNPPh) were prepared. The complex (PNPPhH)RuCl2 (1) was treated with 2 equiv AgOTf to produce the triflate complex (PNPPhH)Ru(OTf)2 (2). Complex 1 was also treated with an excess of NaBH4 to give a bimetallic complex [(PNPPh)RuH3]2 (3). A number of methods, including X-ray crystallography, NMR spectroscopy, and computational studies, were used to probe the structure of 3. Addition of Lewis bases to 3 resulted in octahedral complexes containing a hydride ligand trans to a dihydrogen ligand.
Book Synopsis A Versatile Approach to Transition Metal Complexes Bearing Protic NH, NH-NHC Ligands by the Oxidative Addition of Neutral 2-halogenoazoles by : Rajorshi Das
Download or read book A Versatile Approach to Transition Metal Complexes Bearing Protic NH, NH-NHC Ligands by the Oxidative Addition of Neutral 2-halogenoazoles written by Rajorshi Das and published by . This book was released on 2014 with total page 121 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Book Synopsis Late Transition Metal Complexes Containing Tridentate Pincer-type 1, 3-bis (o-diphenylphosphino) Phenyl)-N, N'-heterocyclic Phosphenium/carbene Ligands by : Baofei Pan
Download or read book Late Transition Metal Complexes Containing Tridentate Pincer-type 1, 3-bis (o-diphenylphosphino) Phenyl)-N, N'-heterocyclic Phosphenium/carbene Ligands written by Baofei Pan and published by . This book was released on 2006 with total page 175 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Book Synopsis The Synthesis, Characterization, and Reactivity of First-row Late Transition Metal Complexes Containing Tridentate Pincer-type N-heterocyclic Phosphenium Ligands by : Sadie E. Knight
Download or read book The Synthesis, Characterization, and Reactivity of First-row Late Transition Metal Complexes Containing Tridentate Pincer-type N-heterocyclic Phosphenium Ligands written by Sadie E. Knight and published by . This book was released on 2015 with total page 276 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Book Synopsis Transition-metal Complexes Bearing Normal, Abnormal and Remote Carbenes by : Yannick D. Bidal
Download or read book Transition-metal Complexes Bearing Normal, Abnormal and Remote Carbenes written by Yannick D. Bidal and published by . This book was released on 2015 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt:
Book Synopsis Elucidating the Electronic Structure of Transition Metal Complexes Featuring Redox Active Ligands by : Linus Kai Ho Chiang
Download or read book Elucidating the Electronic Structure of Transition Metal Complexes Featuring Redox Active Ligands written by Linus Kai Ho Chiang and published by . This book was released on 2014 with total page 187 pages. Available in PDF, EPUB and Kindle. Book excerpt: In this thesis a number of projects involving the design and characterization of complexes bearing redox active ligands are described. Focusing on the phenolate containing ligands, the properties and electronic structure of their corresponding metal complexes were studied by a series of experimental (i.e. electrochemistry, UV-Vis-NIR, EPR, rR etc.) and theoretical (DFT) methods. Specifically, the redox processes of these metal complexes were tuned by varying the para-ring substituents. In one study, nickel-salen (salen is a common abbreviation for N2O2 bis-Schiff-base bis-phenolate ligands) complexes were investigated, where the oxidation potentials of the ligand were predictably decreased as the electron donating ability of the para-ring substituents was increased (NMe2 > OMe > tBu > CF3). Interestingly, the oxidation of these geometrically-symmetric complexes afforded an asymmetric electronic structure in a number of cases, in which the ligand radical was localized on one phenolate rather than delocalized across the ligand framework. This difference in electronic structure was found to be dependent on the electron donating ability of the substituents; a delocalized ligand radical was observed for electron-withdrawing substituents and a localized ligand radical for strongly donating substituents. These studies highlight that para-ring substituents can be used to tune the electronic structure (metal vs. ligand based, localized vs. delocalized radical character) of metallosalen complexes. To evaluate if this electronic tuning can be applied to the metal center, a series of cobalt complexes of these salen ligands were prepared. Indeed, the electronic properties of the metal center were also significantly affected by para-ring substitution. These cobalt-salen complexes were tested as catalysts in organometallic radical-mediated polymerizations, where the most electron rich complexes displayed the best conversion rates. With a firm understanding of the role that the para-ring substituent can play in influencing the electronic structure and reactivity of metallosalen complexes in catalysis, two novel iron complexes, which contain a number of redox active phenolate fragments, were prepared. In addition, these iron-complexes feature a chiral bipyrrolidine backbone. Ligands with this chiral diamine backbone bind metals ions diastereoselectively owing to its increased rigidity, which is critical to stereoselectivity in catalysis. A symmetric (with two phenolates) ligand was prepared by reported methods, and a novel route to synthesize an asymmetric ligand (one phenolate and one pyridine) from symmetric starting materials was established. The neutral iron-complexes were found to be high spin (S = 5/2), and can undergo ligand based oxidation to form an antiferromagnetically-coupled (Stotal = 2) species. The results presented will serve as the basis for catalyst development using complexes of similar ligands.
