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Book Synthesis and Reactivity of Unusual Palladium  II  Complexes Supported by a Diarylamido BIS Phosphine  PNP Pincer Ligand

Download or read book Synthesis and Reactivity of Unusual Palladium II Complexes Supported by a Diarylamido BIS Phosphine PNP Pincer Ligand written by Rafael Huacuja and published by . This book was released on 2015 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: This dissertation discusses the synthesis and reactivity of divalent palladium complexes supported by diarylamido bis-phosphine pincer ligands (PNP). The PNP is a tridentate pincer type ligand which typically adopts meridional type coordination. The rigidity and tight coordination of the PNP ligand provides the unique opportunity to study the coordination of ligands such as O2 and C2H4 to a single coordination site on palladium, or the reactivity of a single empty coordination site trans to a weak trans-influencing ligand such as diarylamido. Irradiation of [(^(F)PNP^(iPr))Pd-]2 under an atmosphere of dioxygen irreversibly produces a mixture of a monohapto palladium(II) superoxide ((^(F)PNP^(iPr))PdO2) and a palladium micro-peroxide ([(^(F)PNP^(iPr))PdO-]2). Under photolytic conditions these two complexes are in equilibrium with each other. (^(F)PNP^(iPr))PdO2, an open-shell paramagnetic species, was characterized by a combination of single-crystal X-ray crystallography, EPR, and 19F NMR spectroscopies. In addition, irradiation of [(PNP)Pd-]2 under an atmosphere of C2H4 produces a mixture of [(PNP)Pd-]2 and a ethylene-bridged dinuclear palladium complex ([(PNP)Pd-CH2-]2). If the ethylene headspace is removed, and [(PNP)Pd-CH2-]2 is irradiated it is completely converted to [(PNP)Pd-]2. This suggests that in the presence of ethylene these two complexes are in photolytic equilibrium with each other. In addition, this dissertation will also discuss the synthesis and reactivity of [(PNPR)Pd]+ (R = ^(i)Pr, ^(t)Bu) cations. [(^(F)PNP^(iPr))Pd]+ cations are highly electrophilic complexes that are able to coordinate Lewis bases such as THF, H2O, and even extremely poor Lewis bases such as toluene and benzene. In addition, irradiation of [(^(F)PNP^(iPr))Pd]+ cations in bromobenzene induces the abstraction of a bromine atom from bromobenzene, consistent with a metalloradical species. Addition of dioxygen to [(^(F)PNP^(iPr))Pd]+ cations generates a paramagnetic, cationic [eta]1 superoxide. In non-halogenated arene solvents [(^(F)PNP^(iPr))Pd]+ cations undergo a highly unusual photo-induced isomerization of the isopropyl groups on the supporting phosphines to n-propyl. This unprecedented isomerization is believed to occur via C-P bond cleavage and is driven by the decrease in sterics around the metal, which allows for the facilitated coordination of the arene solvent. The electronic version of this dissertation is accessible from http://hdl.handle.net/1969.1/152457

Book Synthesis and Reactivity of Nickel  Palladium  and Platinum Phosphine Complexes with Hydridoamido  Hydridophenoxo  and Dithiooxalato Ligands

Download or read book Synthesis and Reactivity of Nickel Palladium and Platinum Phosphine Complexes with Hydridoamido Hydridophenoxo and Dithiooxalato Ligands written by Robert L. Cowan and published by . This book was released on 1989 with total page 358 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Book Design and Synthesis of Metal Phosphine Complexes of Palladium ii  and Gold i  with Various Receptor Ligands for Ion Controlled Or Photoresponsive Host Guest Chemistry

Download or read book Design and Synthesis of Metal Phosphine Complexes of Palladium ii and Gold i with Various Receptor Ligands for Ion Controlled Or Photoresponsive Host Guest Chemistry written by Hau-San Tang and published by Open Dissertation Press. This book was released on 2017-01-27 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: This dissertation, "Design and Synthesis of Metal Phosphine Complexes of Palladium(II) and Gold(I) With Various Receptor Ligands for Ion-controlled or Photoresponsive Host-guest Chemistry" by Hau-san, Tang, 鄧巧珊, was obtained from The University of Hong Kong (Pokfulam, Hong Kong) and is being sold pursuant to Creative Commons: Attribution 3.0 Hong Kong License. The content of this dissertation has not been altered in any way. We have altered the formatting in order to facilitate the ease of printing and reading of the dissertation. All rights not granted by the above license are retained by the author. Abstract: Abstract of thesis entitled DESIGN AND SYNTHESIS OF METAL PHOSPHINE COMPLEXES OF PALLADIUM(II) AND GOLD(I) WITH VARIOUS RECEPTOR LIGANDS FOR ION-CONTROLLED OR PHOTORESPONSIVE HOST-GUEST CHEMISTRY Submitted by Tang Hau San for the Degree of Doctor of Philosophy at The University of Hong Kong in August 2006 A series of palladium(II) phosphine complexes containing different receptor sites, [Pd(PPh R) Cl] [R = C H NHCOCH, C H N(CH )COCH, 2 2 2 6 4 3 6 4 3 3 C HNHCONHPh, C HNHCOPyr and C H NHCO(CH )Pyr] have been 6 4 6 4 6 4 2 3 prepared. Two X-ray crystal structures have been determined, in which one of the crystal structures showed hydrogen bonding interactions between the amide protons and the Cl ions with distances of ca. 2.466 A. The photophysical properties of these complexes have been studied and their emission origins were elucidated. The binding properties of the complexes towards anions have 1 31 been studied by H NMR, P NMR, UV-vis and emission spectrophotometry, in which drastic changes in the ratio of trans to cis isomers upon addition of 31 anions were observed in the P NMR titration studies. The present ion-induced conformational change involving a trans-cis isomerization of the square-planar palladium(II) complex via the binding of anions to amide or urea functionalities through hydrogen bonding interactions represents a new class of ion-controlled switching devices based on transition metal systems. A series of gold(I) alkynyl phosphine complexes containing azobenzene or stilbene functionalities, [{Au(PPh )} (C≡C-L-C≡C)] and [Au (P DEGREESP) (C≡C-L- 3 2 4 2 C≡C) ] [L = C H -N=N-C H or C H -CH=CH-C H; P DEGREESP = dppm, dcpm, 2 6 4 6 4 6 4 6 4 Ph PN(C H F-p)PPh, Ph PN( Pr)PPh, Ph PN(C H )PPh] have been 2 6 4 2 2 2 2 14 29 2 synthesized and characterized. The X-ray crystal structure of [Au (dppm) (C≡C- 4 2 L-C≡C) ] revealed that the two azobenzene ligands in the tetranuclear complex adopted a trans disposition with the presence of short intramolecular Au Au contacts. The azobenzene-containing gold(I) complexes showed emissions both in dichloromethane solution at room temperature and in 77 K glass, which were assigned as a metal-perturbed intraligand (IL) origin mainly derived from the π-π*(C≡C) states with some mixing of a π-π* character of the azo unit. On the other hand, the emissive origin of the stilbene-containing gold(I) complexes was assigned as derived from the π-π* excited state of the stilbene moiety with some mixing of the alkynyl units, and probably mixed with σ(Au-P) → π*(C≡C) excited state in the solid states. The photoisomerization properties of the dinuclear and tetranuclear complexes have been studied, in which a tetranuclear macrocyclic gold(I) alkynyl phosphine complex was demonstrated to function as a dual input molecular logic with photoswitching behaviour that could be controlled by addition or removal of silver(I). In addition, several gold(I) complexes with different crown ether pendants including the mercapto-azacrown ether-containing complexes, [Au (P DEGREESP)(S-A15C5) ] [P DEGREESP = dppm, dcpm] and the mononuclear gold(I) alkynyl 2 2 complexes, [Au(PPh )(C≡CR)] [R = B15C5, B15S5], and dinuclear gold(I) complexes with oligo(ethylene oxide) linkages, [{(Ph P)

Book Reactivity of P H Group of Phosphorus Based Compounds

Download or read book Reactivity of P H Group of Phosphorus Based Compounds written by Kolio D. Troev and published by Academic Press. This book was released on 2017-09-06 with total page 465 pages. Available in PDF, EPUB and Kindle. Book excerpt: Reactivity of P-H Group of Phosphorus Based Compounds bridges the gap between inorganic and organic phosphorus compounds, providing a basis to explore the myriad possibilities for synthesis of novel low and high molecular phosphorus-containing compounds. It covers well-documented reactions in detail, including: tautomerization, oxidation, reduction, alkylation, oxidation coupling, addition reaction to: carbon-carbon multiple bonds, Schiff base, isocyanates, nitriles, epoxides; addition to carbonyl group, Kabachnik- Fields reaction, cross-coupling reaction and more. In an accessible style complete with synthetic routes and figures, the resource then covers the reactivity of multiple P-H group members: phosphines, phosphine oxides, hypophosphorus acid, H-phosphinic acids and polys(alkylene H-phosphonate). This valuable coverage supports the advancement of research and applications in this area for scientists solving a scientific problem or starting a variety of new projects, such as a new reaction for the synthesis of biologically active compounds, new methods of polymer synthesis or a new methodology for polymer modification. Describes the diverse reactivity of the phosphorus-hydrogen group, perhaps the most powerful in organic chemistry Includes practical information for the synthesis of catalysts, biologically active substances, flame retardants, advance materials and polymer materials Offers a visually-accessible guide to important reactions by an internationally recognized chemist

Book Synthesis and Application of Air Stable Secondary Phosphine Oxide  Oxime  and Amine Phosphine Palladium II  Complexes in Transfer Hydrogenation and Cross Coupling Reactions

Download or read book Synthesis and Application of Air Stable Secondary Phosphine Oxide Oxime and Amine Phosphine Palladium II Complexes in Transfer Hydrogenation and Cross Coupling Reactions written by Jason E. Bara and published by . This book was released on 2022 with total page 0 pages. Available in PDF, EPUB and Kindle. Book excerpt: Catalysis plays an important role in industry as over 90% of chemical processes involve catalysts in at least one step. Historically, heterogeneous catalysis has been more commonly employed in industry as these systems tend to be more economically friendly and environmentally benign. However, improved procedures for homogeneous catalysis using organocatalysts and organometallic compounds has generated increased interest in homogeneous systems. Organometallic compounds offer higher specific activities and selectivity in comparison to traditional heterogeneous systems. These qualities make homogeneous catalysis particularly attractive for the production of fine chemicals, pharmaceuticals, and natural products. Ligand design is critical for the development of homogeneous catalysts. For late-transition-metal-catalyzed cross-coupling reactions that rely on C-X or C-H oxidative addition, strongly electron-donating and sterically demanding ligands afford the most efficient systems. Several privileged classes of ligands have been identified and employed in palladium-catalyzed reactions. These systems are believed to promote their respective reactions through a monoligated palladium(0) species. Our work focused on the development of precatalysts with an established 1:1 L:Pd ratio. Specifically, we were interested in the synthesis of palladium(II) precatalysts with the general formula (R3P)Pd(amine)Cl2, using di-tert-butylneopentylphosphine and trineopentylphosphine. Under optimized conditions, the precatalysts were effective for the Buchwald-Hartwig amination of aryl bromides and aryl chlorides. We discovered that the identity of the amine ligand significantly impacts catalyst efficiency with linear primary alkyl amines providing the most active catalysts. A comparison study between the air-stable precatalysts and in situ generated catalysts showed improved activity for the precatalysts. Typically, the aforementioned privileged classes of ligands behave as spectators during the bond activation process. However, ligands containing functional groups that introduce acidic/basic sites proximal to the metal center can participate through acid-base interactions with the substrates. Multifunctional ligands have proven to be efficient in numerous transition-metal-catalyzed processes. We focused on synthesizing secondary phosphine oxide and oxime ligands that contain a basic hydroxyl group(s) upon complexation. The synthesis of oxime-derived palladacycles was facile and efficient. These catalysts efficiently facilitated the transfer hydrogenation of benzophenone. The active species is believed to be a three- or four-atom palladium cluster resulting from decomposition of the palladium-oxime complex.

Book Organic Synthesis with Palladium Compounds

Download or read book Organic Synthesis with Palladium Compounds written by Jiro Tsuji and published by Springer Science & Business Media. This book was released on 2012-12-06 with total page 221 pages. Available in PDF, EPUB and Kindle. Book excerpt: Around 30 years ago the transition metal chemistry received great impulses. In the focus have been reactions of nickel and cobalt and herein especially their carbonyls. Also industrial processes have been developed. When the technical oxidation of ethylene with palladium chloride had been discovered, and a great number oflaboratory reactions, many groups have turned towards this subject. Apart from two important industrial processes - acetaldehyde and vinylacetate from ethylene - a great number of conversions and catalytic reactions with palladium compounds have been researched. Their mechanisms have been cleared up and have con tributed to a better understanding of the complex chemistry of palladium. Last but not least these reactions have also served for more understanding of organic transition metal compounds and catalyses in general. Numerous conventional reactions appear today in a different light. The effects of co-

Book Higher Oxidation State Organopalladium and Platinum Chemistry

Download or read book Higher Oxidation State Organopalladium and Platinum Chemistry written by Allan J. Canty and published by Springer. This book was released on 2011-02-25 with total page 195 pages. Available in PDF, EPUB and Kindle. Book excerpt: 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.

Book Synthesis and Structure of Platinum and Palladium Tertiary Phosphine Complexes

Download or read book Synthesis and Structure of Platinum and Palladium Tertiary Phosphine Complexes written by Matthew D. Sargent and published by . This book was released on 1997 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt:

Book Part 1    eta 3 norcamphene Allyl  Palladium  2   Phosphine Species

Download or read book Part 1 eta 3 norcamphene Allyl Palladium 2 Phosphine Species written by Kurt Blaine Gundlach and published by . This book was released on 1986 with total page 446 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Book Palladium Reagents and Catalysts

Download or read book Palladium Reagents and Catalysts written by Jiro Tsuji and published by Wiley. This book was released on 2004-06-25 with total page 670 pages. Available in PDF, EPUB and Kindle. Book excerpt: Jiro Tsuji, one of the pioneers in this field of organic synthesis, provides synthetic organic chemists with a remarkable overview of the many applications of organopalladium chemistry. Tsuji discusses the recent developments in the field as well as the explosive growth over the last five years. Highlighting the most recent discoveries in this rapidly expanding field, the book; Focuses on new aspects of organopalladium chemistry, putting emphasis on synthetic applications Investigates the new perspectives on the synthetic uses of contemporary organopalladium chemistry This volume, together with Innovations in Organic Synthesis, Tsuji's previous title, provides complete coverage of over 40 years of organopalladium chemistry. Palladium Reagents and Catalysts: New Perspectives for the 21st Century is an essential reference source and companion for students, and both industrial and academic research chemists working in organic synthesis, particularly on synthesis of natural products and medicinal compounds. Those studying development of new synthetic methodology and organometallic chemistry will also find this book valuable.

Book Synthesis  Reactivity  and Catalytic Applications of Ruthenium and Palladium Complexes Supported by New Pincer Ligands

Download or read book Synthesis Reactivity and Catalytic Applications of Ruthenium and Palladium Complexes Supported by New Pincer Ligands written by Morgan C. MacInnis and published by . This book was released on 2011 with total page 504 pages. Available in PDF, EPUB and Kindle. Book excerpt: ABSTRACT continued: These transfer hydrogenation studies are among the first catalytic studies of silyl-pincer complexes and establish [R-PSiP]M species as viable candidates for catalysis. The synthesis and reactivity of 4- and 5-coordinate RuII complexes featuring the [Cy-PSiP] ligand were explored. Reaction of [Cy-PSiP]H with [(p-cymene)RuCl2]2 in the presence of NEt3 and PCy3 resulted in the formation of ([Cy-PSiP]RuCl)2, which serves as a precursor to a series of unprecedented 4-coordinate, formally 14-electron [Cy-PSiP]RuX (X = NHAr, N(SiMe3)2, OtBu) complexes that feature an unusual trigonal pyramidal geometry at Ru. The reactivity of these novel diamagnetic complexes is described, including the reaction of [Cy-PSiP]RuOtBu with amine-boranes resulting in the formation of rare bis(?-BH) complexes. Computational studies confirmed the key role of the strongly ?-donating silyl group of the Cy-PSiP ligand in facilitating the synthesis of such low-coordinate Ru species and enforcing the unusual trigonal pyramidal geometry. The mechanism of ammonia-borane activation was also examined computationally. Lastly, the synthesis and structural characterization of PdII complexes supported by the pincer-like bis(amino)phosphido ligand [?3-(2-Me2NC6H4)2P]- ([NPN]) is described. Examples of ?1-, ?2-, and ?3-NPN coordination to Pd are described, as is the catalytic activity of ([NPN]PdX)2 (X = Cl, OAc, OTf) complexes in the Heck olefin arylation reaction. In an effort to discourage the formation of phosphido-bridged dinuclear complexes, pre-coordination of the Lewis acid BPh3 to [NPN] was pursued. Upon reaction of [N(P?BPh3)N]K with [PdCl(C3H5)]2, the ?1-allyl complex [?3-N(P?BPh3)N]Pd(?1-C3H5) was isolated, which establishes the coordination of a Lewis acid to the phosphido donor of the [NPN] ligand as a viable strategy for encouraging the formation of mononuclear ?3-NPN complexes.

Book Synthesis  Reactivity  and Catalysis of 3 iminophosphine Palladium Complexes

Download or read book Synthesis Reactivity and Catalysis of 3 iminophosphine Palladium Complexes written by Andrew Ronald Shaffer and published by . This book was released on 2009 with total page 456 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Book Inorganic Syntheses  Volume 23

Download or read book Inorganic Syntheses Volume 23 written by and published by John Wiley & Sons. This book was released on 2009-09-22 with total page 284 pages. Available in PDF, EPUB and Kindle. Book excerpt: The volumes in this continuing series provide a compilation of current techniques and ideas in inorganic synthetic chemistry. Includes inorganic polymer syntheses and preparation of important inorganic solids, syntheses used in the development of pharmacologically active inorganic compounds, small-molecule coordination complexes, and related compounds. Also contains valuable information on transition organometallic compounds including species with metal-metal cluster molecules. All syntheses presented here have been tested.

Book Synthesis  Structure  and Reactivity of New Palladium III  Complexes

Download or read book Synthesis Structure and Reactivity of New Palladium III Complexes written by Michael Glenn Campbell and published by . This book was released on 2014 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: Palladium is one of the most common and versatile transition metals used in modern organometallic chemistry. The chemistry of palladium in its 0, +II, and +IV oxidation states is well-known; by comparison, the chemistry of palladium in its +III oxidation state is in its infancy. The work in this thesis involves the study of previously unknown Pd(III) complexes, including applications in materials chemistry and catalysis.

Book Handbook of Organopalladium Chemistry for Organic Synthesis

Download or read book Handbook of Organopalladium Chemistry for Organic Synthesis written by Ei-ichi Negishi and published by John Wiley & Sons. This book was released on 2003-11-24 with total page 1697 pages. Available in PDF, EPUB and Kindle. Book excerpt: Organized to provide maximum utility to the bench synthetic chemist. The editor is well-known for his work in exploring, developing, and applying organopalladium chemistry. Contributors include over 24 world authorities in the field.