Download or read book Synthesis and Reactivity of Ruthenium Phosphine Complexes Containing Metal carbon and Metal heteroatom Bonds written by Melinda Jane Burn and published by Ann Arbor, Mich. : University Microfilms International. This book was released on 1993 with total page 424 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Download or read book Synthesis and Reactivity of Compounds Containing Ruthenium carbon nitrogen and oxygen Bonds written by and published by . This book was released on 1990 with total page 417 pages. Available in PDF, EPUB and Kindle. Book excerpt: 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.

Download or read book Ruthenium in Organic Synthesis written by Shun-Ichi Murahashi and published by John Wiley & Sons. This book was released on 2006-03-06 with total page 398 pages. Available in PDF, EPUB and Kindle. Book excerpt: 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)

Download or read book Synthesis Characterization and Reactivity of Ruthenium Porphyrin Complexes Containing Metal carbon Bonds microform written by Mingzhe Ke and published by National Library of Canada. This book was released on 1988 with total page 444 pages. Available in PDF, EPUB and Kindle. Book excerpt:

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)

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.

Download or read book Synthesis and Reactivity of Compounds Containing Ruthenium carbon nitrogen and oxygen Bonds written by John Frederick Hartwig and published by . This book was released on 1990 with total page 434 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Download or read book Recent Advances in Hydride Chemistry written by Maurizio Peruzzini and published by Elsevier. This book was released on 2002-01-30 with total page 577 pages. Available in PDF, EPUB and Kindle. Book excerpt: This book has been conceived to collect the most important recent advances in all areas of hydride chemistry research, including chemical reactivity, instrumental investigation, theory, and applications in the areas of catalysis, biochemistry and materials science. Many of the chapters have been written by the plenary lecturers of the EURO-Hydrides 2000 conference, but other leading scientists in this field have also been invited to contribute. The first part of the book focuses on the chemistry and catalysis of transition metal hydrides. Another block of chapters illustrates the most recent advances in the application of instrumental techniques to the study of the properties and reactivity of hydride compounds. The final part of the book illustrates the relevance of metal-hydrogen bonds in biochemistry and materials science. All of the chapters of this book have been evaluated by independent reviewers.

Download or read book Synthesis Characterization and Reactivity of Ruthenium Phosphine and Rhodium Heterobimetallic P N P Complexes written by Robert John McNair and published by . This book was released on 1985 with total page 502 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Download or read book Synthesis Structures and Spectroscopic Properties of Primary and Secondary Phosphine Complexes of Iron Ruthenium and Osmium Porphyrins written by Jin Xie 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, "Synthesis, Structures and Spectroscopic Properties of Primary and Secondary Phosphine Complexes of Iron, Ruthenium and Osmium Porphyrins" by Jin, Xie, 解錦, 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 SYNTHESIS, STRUCTURES AND SPECTROSCOPIC PROPERTIES OF PRIMARY AND SECONDARY PHOSPHINE COMPLEXES OF IRON, RUTHENIUM AND OSMIUM PORPHYRINS Submitted by XIE JIN For the degree of Doctor of Philosophy at The University of Hong Kong in Oct 2007 Primary and secondary phosphine complexes of transition metals are of fundamental importance in metal-mediated P-H bond functionalization, phosphido/phosphinidene formation, and have applications in materials science. This thesis mainly describes the first isolation of primary and secondary phosphine complexes of a metalloporphyrin, along with their spectral, structural, and redox properties. The reactivity of primary and secondary phosphines coordinated to metalloporphyrins, particularly their hydrophosphination reactions with C=C bonds, is included. Investigations on the attempted approach to metal primary phosphine complexes bearing a pentapyridyl ligand (PY5) are also included. Ruthenium and osmium porphyrins form isolable complexes with primary and II secondary phosphines. Complexes [Ru (por)(PH Ph )] and n 3-n 2 II II [Os (por)(CO)(PH Ph )] (n = 1, 2) were prepared from reaction of [M (por)(CO)] n 3-n VI (M = Ru, Os) with excess PH Ph or PHPh . Reaction of [Os (por)O ] with PHPh 2 2 2 2 II mainly generated [Os (por){P(OH)Ph }(PHPh )], with concomitant formation of 2 2 II minor amounts of [Os (por){P(OH)Ph } ]. The bis-(primary phosphine) complex 2 2 II [Ru (F -tpp)(PH Ph)] is strikingly stable toward air and features reversible 20 2 2 +/0 Ru(II)/Ru(III) oxidation couple at E = 0.39 V vs Cp Fe . NMR spectrum 1/2 2 simulation revealed a strong coupling between the trans P nuclei in II 2 2 [Ru (por)(PH Ph ) ] (n = 1, 2; J ≈ 500 Hz). A J value of 467 Hz was directly n 3-n 2 PP PP 31 II obtained from the proton-decoupled P NMR spectrum of [Os (F - 20 tpp){P(OH)Ph }(PHPh )], which is much larger than that observed for the trans 2 2 phosphines in a non-porphyrin osmium phosphine complex. A one-pot synthesis of metal primary phosphine complexes from user-friendly O=PClR and PClR has been realized by treating these precursors with 2 2 II [Ru (por)(CO)] and LiAlH, leading to the isolation of primary alkylphosphine II complexes of ruthenium porphyrins, [Ru (por)(PH R) ] (por = ttp, 4-MeO-ttp, F -tpp; 2 2 20 t sec R = Ad, Bu, Bu), which are the first examples of primary alkylphosphine complexes of ruthenium. II Reactions of [Ru (F -tpp)(PH Ph ) ] (n = 1, 2) with CH =CHR (R = CO Et, 20 n 3-n 2 2 2 t II CN) in the presence of BuOK afforded [Ru (F -tpp){P(CH CH R) Ph } ] in high 20 2 2 n 3-n 2 yields. This is the first observation of alkene hydrophosphination by primary/secondary phosphines coordinated to a metalloporphyrin. The reactions of III [Fe (por)Cl] (por = F -tpp, 2,6-Cl tpp) with Na S O followed by treatment with 20 2 2 2 4 excess PH Ph, PHPh, or PH Ad led to the isolation of the first examples of iron 2 2 2 porphyrin complexes of primary and secondary phosphines, of which the primary phosphine complexes underwent partial dissociation in solutions at room temperature. Treatment of PY5 (or PY5-OH) with Ag(p-MeC H SO), AgNO, or 6 4 3 3 [Cu(MeCN) ]PF resulted in the isolation of [Ag (L) ]X (L = PY5 or PY5-OH, X = 4 6 2 2 2 - - I p-MeC H SO or NO ) and [Cu (PY5)(MeCN)]PF, which adopt two types of 6 4 3 3 6

Download or read book Synthesis Characterization and Reactivity of Rhodium and Iridium Phosphine Complexes Containing Sulfur Ligands Resulting from Reactions with H2S written by Ann Marie Mueting and published by . This book was released on 1985 with total page 586 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Download or read book Synthesis and Reactivity of Ruthenium and Platinum Complexes with Non dative Heteroatomic Ligands Studies of Carbon hydrogen Bond Activation written by and published by . This book was released on 2004 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: 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).

Download or read book Ruthenium Complexes Containing Phosphine phosphine Oxide Ligands written by and published by . This book was released on 2011 with total page 41 pages. Available in PDF, EPUB and Kindle. Book excerpt: RuCl3(NO)(PPh3)2 reacts with two equivalents of Ph2PCH2P(O)Ph2 (dppmO) or Ph2P(CH2)2P(O)Ph2 (dppeO). In these reactions both triphenylphosphines on the ruthenium metal are replaced with ligands. RuCl3(NO)(dppmO)2 and RuCl3(NO)(dppeO)2 were characterized with IR and NMR spectroscopy, as well as x-ray crystallography. The complexes are octahedral with the two coordinated ligands trans to one another, displaying AA'XX' spin systems. Coupling constants and chemical shifts were determined by simulations using Spinworks. Both complexes can also be synthesized by heating two equivalents of ligand with one equivalent of RuCl3(NO)H2O. A chloride can be abstracted from RuCl3(NO)(dppmO)2 when reacted with AgBF4. NMR spectra indicate that the removal of a chloride allows the phosphoryl oxygen of the ligand to coordinate to the open site. A complex containing the same cation can be synthesized by reaction of a 2:1 molar ratio of dppmO and RuCl3(NO)H2O at room temperature. Both products have been characterized using IR and NMR spectroscopy, and x-ray crystallography in the case of the RuCl3(NO)H2O reaction. Crystals of [RuCl2(dppeO)2]+BF4- were obtained from the reaction of RuCl3(NO)(dppeO)2 and excess AgBF4. In this reaction NO+ is abstracted and Ru(II) is oxidized to Ru(III). Preliminary 31P data indicates that there are other products in this reaction. The differences in catalytic abilities of these complexes have yet to be determined.

Download or read book Synthesis and Reactivity of Ruthenium and Platinum Complexes with Non dative Heteroatomic Ligands written by Yuee Feng and published by . This book was released on 2007 with total page 202 pages. Available in PDF, EPUB and Kindle. Book excerpt: Keywords: non-dative heteroatomic ligands, hydrogen atom abstraction, deprotonation, C-H activation, platinum, ruthenium, organometallic.

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

Download or read book Synthesis and Reactivity of Ruthenium II and Osmium II Organometallic Imido Complexes written by Richard Ira Michelman and published by . This book was released on 1992 with total page 344 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Download or read book Synthesis and Reactivity of Rhenium and Technetium Polyaryl Complexes written by Christopher Alan Morse and published by . This book was released on 1998 with total page 334 pages. Available in PDF, EPUB and Kindle. Book excerpt: