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Transition Metal Complexes With Pn Ligands And Silylenes Synthesis And Catalytic Studies
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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 N-heterocyclic Silyl and Silylene Metal Complexes Within a PSIP Framework by : Amy Marie Jehl
Download or read book N-heterocyclic Silyl and Silylene Metal Complexes Within a PSIP Framework written by Amy Marie Jehl and published by . This book was released on 2019 with total page 237 pages. Available in PDF, EPUB and Kindle. Book excerpt: N-heterocyclic carbenes (NHC) are strong Lewis bases that have demonstrated broad utility as ligands for transition metal (TM) catalysts. Silicon analogues, N-heterocyclic silylenes (NHSi), are comparatively less well studied. The decreased [Pi]-[pi] overlap between the Si 3p orbital and adjacent nitrogen lone pairs creates a more accessible vacant orbital on Si, resulting in increased ambiphilic character. When bound to a transition metal, this empty orbital presents an opportunity to cooperatively bind and activate substrate molecules. To increase the stability of a potential metal-silylene complex we targeted the diphosphine ligand precursor 1,2-bis(R2PCH2NCH2)C6H4 (R = alkyl or aryl), first reported by Yamashita and Nozaki in the construction of a boron-anchored pincer. Reported here are (PCy)2Si pincer ligands and their TM-silylene complexes for small molecule activation.
Book Synopsis Synthesis, Reactivity, and Catalytic Studies of Transition Metal Complexes of Chelating Cyclic and Acyclic Diaminocarbene Ligands by : Yoshitha Anju Wanniarachchi
Download or read book Synthesis, Reactivity, and Catalytic Studies of Transition Metal Complexes of Chelating Cyclic and Acyclic Diaminocarbene Ligands written by Yoshitha Anju Wanniarachchi and published by . This book was released on 2008 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt:
Book Synopsis Transition Metal Carbyne Complexes by : F.R. Kreißl
Download or read book Transition Metal Carbyne Complexes written by F.R. Kreißl and published by Springer Science & Business Media. This book was released on 2012-12-06 with total page 274 pages. Available in PDF, EPUB and Kindle. Book excerpt: The chemistry of transition metal carbyne complexes has become a highly attractive field during the past twenty years. In recent years its application to aspects of catalysis and metathesis has gained considerable interest from inorganic as well as organic chemists. In addition, organic synthesis by means of metal carbon multiple bond reagents offers the most sophisticated technology currently available. In consideration of these developments some of Professor E. O. Fischer's former coworkers and colleagues felt obliged to orga nize this NATO Advanced Research Workshop on Transition Metal Carbyne Complexes in the Bavarian Alps. They have been encouraged by the fact that most of the distinguished scientists in the field of metal-carbon multiple bond chemistry had finally agreed to participate and to present stimulating lectures. The organizers of the workshop are deeply grateful to the Scientific Affairs Division of the NATO for the generous financial support of the meeting in Wildbad Kreuth and for the preparation of this book. They also feel indebted to acknowledge the generous support from Wacker-Chemie, BASF, Peroxid-Chemie, Hoechst and Bayer. Finally they thank the staff of the Hanns-Seidel-Stiftung in Wildbad Kreuth for providing a pleasant and stimu lating atmosphere during the meeting.
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 Synthesis, Characterization, and Reactivity of Transition Metal Complexes Containing Multi-donor Ligands by : John C. Linehan
Download or read book Synthesis, Characterization, and Reactivity of Transition Metal Complexes Containing Multi-donor Ligands written by John C. Linehan and published by . This book was released on 1986 with total page 514 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Book Synopsis Transition Metals in Coordination Environments by : Ewa Broclawik
Download or read book Transition Metals in Coordination Environments written by Ewa Broclawik and published by Springer. This book was released on 2019-03-16 with total page 532 pages. Available in PDF, EPUB and Kindle. Book excerpt: This book focuses on the electronic properties of transition metals in coordination environments. These properties are responsible for the unique and intricate activity of transition metal sites in bio- and inorganic catalysis, but also pose challenges for both theoretical and experimental studies. Written by an international group of recognized experts, the book reviews recent advances in computational modeling and discusses their interplay using experiments. It covers a broad range of topics, including advanced computational methods for transition metal systems; spectroscopic, electrochemical and catalytic properties of transition metals in coordination environments; metalloenzymes and biomimetic compounds; and spin-related phenomena. As such, the book offers an invaluable resource for all researchers and postgraduate students interested in both fundamental and application-oriented research in the field of transition metal systems.
Book Synopsis Organophosphorus Chemistry by : Viktor Iaroshenko
Download or read book Organophosphorus Chemistry written by Viktor Iaroshenko and published by John Wiley & Sons. This book was released on 2019-01-07 with total page 224 pages. Available in PDF, EPUB and Kindle. Book excerpt: Filling the gap for an up-to-date reference that presents the field of organophosphorus chemistry in a comprehensive and clearly structured way, this one-stop source covers the chemistry, properties, and applications from life science and medicine. Divided into two parts, the first presents the chemistry of various phosphorus-containing compounds and their synthesis, including ylides, acids, and heterocycles. The second part then goes on to look at applications in life science and bioorganic chemistry. Last but not least, such important practical aspects as 31P-NMR and protecting strategies for these compounds are presented. For organic, bioinorganic, and medicinal chemists, as well as those working on organometallics, and for materials scientists. The book, a contributed work, features a team of renowned scientists from around the world whose expertise spans the many aspects of modern organophosphorus chemistry.
Book Synopsis Metallocenes in Regio- and Stereoselective Synthesis by : Marko Hapke
Download or read book Metallocenes in Regio- and Stereoselective Synthesis written by Marko Hapke and published by Springer Nature. This book was released on with total page 208 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Book Synopsis Synthesis, Characterization, and Reactivity of Transition Metal Complexes Supported by Heteropolydentate Ligation by : Adam Ruddy
Download or read book Synthesis, Characterization, and Reactivity of Transition Metal Complexes Supported by Heteropolydentate Ligation written by Adam Ruddy and published by . This book was released on 2014 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt:
Book Synopsis The Catalytic Chemistry of Pi-allyl Transition Metal Complexes with Phosphorus Ligands by : Louis Sheldon Stuhl
Download or read book The Catalytic Chemistry of Pi-allyl Transition Metal Complexes with Phosphorus Ligands written by Louis Sheldon Stuhl and published by . This book was released on 1978 with total page 198 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Book Synopsis The Synthesis and Chemistry of Transition-metal Complexes Incorporating Sila- and Germaaromatic Ligands by : Jeffrey Michael Dysard
Download or read book The Synthesis and Chemistry of Transition-metal Complexes Incorporating Sila- and Germaaromatic Ligands written by Jeffrey Michael Dysard and published by . This book was released on 2000 with total page 492 pages. Available in PDF, EPUB and Kindle. Book excerpt:
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 Synthesis, Characterization, and Computational Studies of Unsaturated Transition Metal Complexes by : Lori Anne Watson
Download or read book Synthesis, Characterization, and Computational Studies of Unsaturated Transition Metal Complexes written by Lori Anne Watson and published by . This book was released on 2004 with total page 504 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Book Synopsis Late Transition Metal Complexes for E-H Bond Activation and Additions to Multiple Bonds by : Kevin Hesp
Download or read book Late Transition Metal Complexes for E-H Bond Activation and Additions to Multiple Bonds written by Kevin Hesp and published by . This book was released on 2010 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt:
Book Synopsis Synthesis, Chemical and Catalytic Properties of Transition Metal Complexes with Polydentate Phosphine Ligands by : Hon-man Lee
Download or read book Synthesis, Chemical and Catalytic Properties of Transition Metal Complexes with Polydentate Phosphine Ligands written by Hon-man Lee and published by . This book was released on 1997 with total page 314 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Book Synopsis Synthesis, Structure and Catalytic Reactivity of Transition Metal Complexes Containing Unsaturated Organosilicon Ligands by : Leo J. Procopio
Download or read book Synthesis, Structure and Catalytic Reactivity of Transition Metal Complexes Containing Unsaturated Organosilicon Ligands written by Leo J. Procopio and published by . This book was released on 1991 with total page 794 pages. Available in PDF, EPUB and Kindle. Book excerpt: