Download or read book Synthesis Characterization and Reactivity of Monomeric Copper I Complexes Possessing Pi donor Ligands written by Samuel A. Delp and published by . This book was released on 2010 with total page 185 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Download or read book The Synthesis Characterization and Reactivity of Copper Nitrosyl Complexes with Sterically Hindered Tris pyrazolyl hydroborate Ligands written by Susan Marie Carrier and published by . This book was released on 1995 with total page 336 pages. Available in PDF, EPUB and Kindle. Book excerpt:

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:

Download or read book Synthesis and Structural Characterization of Copper I Complexes with Hard Donor Ligands written by Björn Gustafsson and published by . This book was released on 2004 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt:

Download or read book Synthesis and structural characterization of complexes between Pi acid ligands and copper I chloride written by Mikael Håkansson and published by . This book was released on 1990 with total page 61 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Download or read book Synthesis Characterization and Reactivity of High valent Copper Complexes of Macrocyclic Tetraamido N Ligands written by Stacy A. Williams and published by . This book was released on 2000 with total page 0 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Download or read book Synthesis and Original Reactivity of Copper and Gold Complexes written by Maximilian Joost and published by Springer. This book was released on 2015-06-13 with total page 244 pages. Available in PDF, EPUB and Kindle. Book excerpt: This thesis addresses the coordination chemistry and reactivity of copper and gold complexes with a focus on the elucidation of (i) the metal-mediated activation of σ-bonds and (ii) the migratory insertion reaction. Both processes are of considerable importance in organometallic chemistry, but remain elusive for Cu and Au complexes. In this work, the author contributes significant advances: The first σ-SiH complexes of copper are experimentally and computationally characterized, yielding valuable insights into σ-bond activation processes for copper. Evidence for a highly unusual migratory syn insertion of unsaturated organic molecules into the gold-silicon bond of silylgold (I) complexes is provided and the corresponding mechanism identified. The intermolecular oxidative addition of σ-SiSi, σ-CC and σ-CX (X=halogen) bonds with molecular gold (I) complexes is studied in detail, effectively demonstrating that this reaction, usually considered to be impossible for gold, is actually highly favored, provided an adequate ligand is employed. The use of small-bite angle bis (phosphine) gold (I) complexes allows for the first time the oxidative addition of σ-CC and σ-CX bonds for gold (I). These results shed light on an unexpected reactivity pattern of gold complexes and may point the way to 2-electron redox transformations mediated by this metal, opening up new perspectives in gold catalysis.

Download or read book Synthesis and Reactivity of Copper Complexes Possessing Non dative Ligands written by and published by . This book was released on 2004 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt:

Download or read book Copper and Silver Complexes in Conjugate Addition written by R. Bryan Scott Klassen and published by . This book was released on 1992 with total page 442 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Download or read book Synthesis and Characterization of Some New Copper I Complexes with Multidentate Ligands Containing Phosphorus Arsenic and Nitrogen Donor Atoms written by Johannes Schmidt and published by . This book was released on 1988 with total page 188 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Download or read book Synthesis and Structural Characterization of Complexes Between Pi acid Ligands and Copper I chloride written by Mikael Hakansson and published by . This book was released on 1990 with total page 61 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Download or read book Synthesis and Reactivity of Copper i Amidinate Complexes written by Andrew C. Lane and published by . This book was released on 2015 with total page 87 pages. Available in PDF, EPUB and Kindle. Book excerpt: Group 11 transition metals are used daily throughout our bodies and as additives in many common products. One biological function of copper, a group 11 metal, is its use in the Cu A site of cytochrome c oxidase, an enzyme found in the last step of cellular respiration. To model this active site, three formamidinate ligands have been examined: 2,6-dimethylphenyl, 2,6- diisopropylphenyl, and 2,4,6-trimethylphenyl. The synthesis and structural characterization of these dinuclear Cu(I) complexes is described as well as their redox chemistry with I 2 to afford complexes of mixed-valence which is the normal resting state of the Cu A site. Using EPR spectroscopy and DFT calculations on the iodine oxidized products, different electronic structures base d on the formamidinate was found. Additionally, insertion of CS 2 into the copper-nitrogen bonds of the copper(I) formamidinate complexes produces tetra- and hexanuclear clusters based on the steric properties of the ligand

Download or read book Synthesis and Reactivity of Copper Complexes Possessing Non dative Ligands written by Elizabeth D. Blue and published by . This book was released on 2006 with total page 194 pages. Available in PDF, EPUB and Kindle. Book excerpt: Presented herein are the isolation and characterization of a number of new copper(I) halide complexes and the first two examples of monomeric copper(I) amido complexes, (dtbpe)Cu(NHPh) and (IPr)Cu(NHPh). These Cu(I) anilido complexes have been shown to be more nucleophilic than a related Ru(II) anilido complex in reactivity studies with bromoethane, and reveal increasing nucleophilicity in the order (SIPr)Cu(NHPh) < (IPr)Cu(NHPh) < (IMes)Cu(NHPh) < (dtbpe)Cu(NHPh). (IPr)Cu(NHPh) is thermodynamically favored over (IPr)Cu(Ph)/NH2Ph or [(IPr)Cu(mu-H)]2/NH2Ph, respectively. Computational studies are consistent with the observed reactivity and indicate strong Cu-N bonds with nucleophilic amido nitrogen.

Download or read book 1 Dioxygen Reactivity of Multinuclear Fluorinated Copper I Alkoxides Facilitated by Secondary Ligand Interactions 2 Synthesis and Characterization of Mononumeric O donor Complexes of Divalent Copper and Zinc written by June S. Lum and published by . This book was released on 2013 with total page 456 pages. Available in PDF, EPUB and Kindle. Book excerpt: Abstract: Abstract: Copper(I) complexes with fluorinated alkoxide ligands with the form K[Cu(OCRMe F2 )2 ], in which R = MeF ( 4 ), Ph (5 ), or Me (6 ), were synthesized and characterized. The dioxygen (O2 ) reactivity of the series of complexes was investigated at -78°C and two stoichiometries of {Cun O 2 }species were observed. Manometric O2 uptake studies showed dinuclear {Cu2 O2 } and triuclear {Cu3 O 2 } species and their chromophores were measured with UV-vis spectroscopy. Warming these species to room temperature resulted in irreversible spectroscopic changes, and ligand hydroxylation was observed for complexes 5 and 6. ESI-MS study of reactions with 18 O 2 confirmed O2 as the source of the ligand hydroxyl O atom. A tetrameric Cu(II) carbonate complex, {{K2 (DME)1.5 }[Cu(OCMeMe F2 )2 CO3 ]}4 (14 ), was obtained from CO2 addition to the {Cu2 O3 } moiety derived from 6. Irreversible reduction of O2 required secondary potassium-ligand (K···F and K-O) interactions which bridge multiple [Cu(OCRMe F2 )2 ]- anions in solid-state structures of 4, 5, and 6, and were quantified by K+ cation bond valence analysis. Solution conductivity studies confirmed that neutral aggregates of K[Cu(OCRMeF2 ) 2 ] complexes are retained in solution. Ionic copper(I) complexes of the form {K(18C6)}[Cu(OCRMeF2 )2 ] in which R = MeF (7 ), Ph (8 ), or Me ( 9 ) and (Ph4 P)[Cu(OCRMeF2 ) 2 ], with R = MeF (10 ) were prepared, none of which react with O2 at -78°C. The Cu(II) alkoxide compounds {K(18C6)}[Cu(OCRMeF 2 )3 ], in which R= MeF (15 ) and Me (16 ) were prepared and spectroscopically and magnetically characterized. Compound 16 was demonstrated to be trigonal-planar by X-ray crystallography and all other data for 15 are consistent with trigonal-planar coordination. Two four-coordinate Cu(II) compounds with dodecafluoropinacolate (ddfp) ligands were also synthesized and characterized spectroscopically. The structurally characterized square-planar ddfp compounds have the form {K(solvent) 2 }2 [Cu(ddfp)2 ], in which solvent = H2 O (17 ) or DME (18 ). Diamagnetic Zn(II) derivatives with aryloxide ligands of the form {K(18C6)} 2 [Zn(OAr)4 ], in which Ar = ArF (19 ) or Ar' (20 ) and {K(18C6)}[Zn(OCRMeF2 ) 3 ], with R = Ph (21 ) were also prepared and characterized by X-ray crystallography and multinuclear NMR.

Download or read book Synthesis and Characterization of Some Copper II Complexes with Ligands Formed with 14 membered Ring Amine Ligands written by Scott Jackson Dantley and published by . This book was released on 1995 with total page 130 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Download or read book Synthesis Characterization and Reactivity Studies of Low coordinate Late Transition Metal Complexes and the Preparation and Characterization of a Low coordinate Samarium Complex written by Pei Zhao and published by . This book was released on 2015 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: This dissertation focuses on the synthesis, characterization and reactivity study of terphenyl ligand stabilized bis([mu]-oxo) dimeric iron and cobalt complexes. The synthesis and characterization of low-coordinate cobalt alkyl and iron alkyl complexes are also described. In addition, it describes the preparation of the first monomeric homoleptic solvent-free bis(aryloxide) lanthanide complex. The solid state structures of new compounds were determined by single crystal X-ray crystallography. Magnetic properties of paramagnetic compounds were measured by superconducting quantum interference device (SQUID) or Evans' methods for solid state or solution phase, respectively. The new compounds were also characterized by UV-Visible spectroscopy. Furthermore, infrared spectroscopy, Mössbauer spectroscopy, electron paramagnetic resonance spectroscopy, mass spectrometry, cyclic voltammetry and elemental analysis were employed to characterize some of the compounds when applicable. In some cases, DFT calculations were applied to elucidate the bonding and energy levels of molecular orbitals in the complexes. In Chapter 2, The bis([mu]-oxo) dimeric complexes {Ar[superscript iPr8]OM([mu]-O)}2 (Ar [superscript iPr8] = -C6H-2,6-(C6H2-2,4,6-[superscript i]Pr3)2-3,5-[superscript i]Pr2; M = Fe or Co) were prepared by oxidation of the metal (I) half-sandwich complexes {Ar[superscript iPr8]M([eta]6-arene)} (arene = benzene or toluene; M = Fe or Co). The iron species {Ar[superscript iPr8]OFe([mu]-O)}2 was prepared by reacting {Ar[superscript iPr8]Fe([eta]6-benzene)} with N2O or O2 and the cobalt species {Ar[superscript iPr8]OCo([mu]-O)}2 was prepared by reacting {Ar[superscript iPr8]Co([eta]6-toluene)} with O2. Both {Ar[superscript iPr8]OFe([mu]-O)}2 and {Ar[superscript iPr8]OCo([mu]-O)}2 were characterized by X-ray crystallography, UV-vis spectroscopy, magnetic measurements and, in the case of the iron species, by Mössbauer spectroscopy. The solid-state structures of both compounds reveal unique M2([mu]-O)2 (M = Fe or Co) cores with formally three-coordinate metal ions. The Fe···Fe separation in {Ar[superscript iPr8]OFe([mu]-O)}2 bears a resemblance to that in the Fe2([mu]-O)2 diamond core proposed for the methane monooxygenase intermediate Q. The structural differences between {Ar[superscript iPr8]OFe([mu]-O)}2 and {Ar[superscript iPr8]OCo([mu]-O)}2 are reflected in rather differing magnetic behavior. Compound {Ar[superscript iPr8]OCo([mu]-O)}2 is thermally unstable and its decomposition at room temperature resulted in the oxidation of the Ar[superscript iPr8] ligand via oxygen insertion and addition to the central aryl ring of the terphenyl ligand to produce the 5,5'-peroxy-bis[4,6-[superscript i]Pr2-3,7-bis(2,4,6-iPr3-phenyl)oxepin-2(5H)-one]. The structure of the oxidized terphenyl species is closely related to that of a key intermediate proposed for the oxidation of benzene. In Chapter 3, the homoleptic, cobalt(I) alkyl [Co{C(SiMe2Ph)3}]2 was prepared by reacting CoCl2 with [Li{C(SiMe2Ph)3}(THF)] in a 1:2 ratio though the initial intent was to synthesize a dialkyl cobalt (II) complex. Attempts to synthesize the corresponding iron(I) species led to the iron(II) salt [Li(THF)4][Fe2([mu]-Cl)3{C(SiMe2Ph)3}2]. Both complexes were characterized by X-ray crystallography, UV-vis spectroscopy, and magnetic measurements. The structure of [Co{C(SiMe2Ph)3}]2 consists of dimeric units in which each cobalt(I) ion is [sigma]-bonded to the central carbon of the alkyl group -C(SiMe2Ph)3 and [pi]-bonded to one of the phenyl rings of the -C(SiMe2Ph)3 ligand attached to the other cobalt(I) ion in the dimer. The structure of [Li(THF)4][Fe2([mu]-Cl)3{C(SiMe2Ph)3}2] features three chlorides bridging two iron(II) ions. Each iron (II) ion is also [sigma]-bonded to the central carbon of a terminal -C(SiMe2Ph)3 anionic ligand. The magnetic properties of [Co{C(SiMe2Ph)3}]2 reveal the presence of two independent cobalt (I) ions with S = 1 and a significant zero-field splitting of D = 38.0(2) cm−1. The magnetic properties of [Li(THF)4][Fe2([mu]-Cl)3{C(SiMe2Ph)3}2] reveal extensive antiferromagnetic exchange coupling with J = -149(4) cm−1 and a large second-order Zeeman contribution to its molar magnetic susceptibility. Formation of the alkyl [Co{C(SiMe2Ph)3}]2 and the halide complex [Li(THF)4][Fe2([mu]-Cl)3{C(SiMe2Ph)3}2] under similar conditions is probably due to the fact that Co(II) is more readily reduced than Fe(II). Some other synthetic routes were also attempted to synthesize a dialkyl cobalt (II) complex and they are described in this chapter. Neither [Co(NPh2)2]2 nor cobaltocene reacts with [Li{C(SiMe2Ph)3}(THF)] to afford a dialkyl cobalt (II) complex. Metathesis reactions of cobalt halides with lithium salts of alkyl ligand HCPh2R (R = -Ph or -SiMe3) resulted in the reduction of cobalt (II) to cobalt metal and the coupling of ligands, which indicate that homolytic cleavage of the cobalt-carbon bond was probably involved in the metathesis reactions. Furthermore, in chapter 4, reaction of Sm[N(SiMe3)2]2(THF)2 with two equivalents of bulky aryloxide ligand HOAr[superscript iPr6] (Ar[superscript iPr6] = -C6H3-2,6-(C6H2-2,4,6-[superscript i]Pr3)2) afforded the first monomeric homoleptic solvent-free bis(aryloxide) lanthanide complex Sm(OAr[superscript iPr6])2. The complex was characterized by crystallography, UV-Visible spectrum, IR and magnetically by the Evans' method. The O-Sm-O angle is bent at 111.08(9)̊. The samarium ion in Sm(OAr[superscript iPr6])2 also shows weak interactions with the flanking aryl rings of the terphenyloxide ligands. The complex is paramagnetic at room temperature with magnetic moment of 3.51 [mu]B.

Download or read book Synthesis AndRreactivity of Copper I Copper II Platinum II and Platinum IV Complexes with Non dative Heteroatomic Ligands written by and published by . This book was released on 2004 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: Examples of late transition metal complexes with amido, alkoxo and sulfido ligands are relatively rare in part due to enhanced reactivity based on nucleophilicity and basicity of the heteroatomic ligand (X). The highly nucleophilic and basic character of formally anionic X ligands coordinated to metal centers with low oxidation states is attributable to the disruption of ligand-to-metal pi-bonding. Examples of common reactivity for these systems include nucleophilic addition reactions, insertions of unsaturated substrates, acid/base chemistry with acidic C-H bonds and C-H activation reactions with aromatic substrates. In addition to fundamental reactivity studies, these complexes also offer opportunities for incorporation into catalytic processes. Late transition metal complexes with non-dative X ligands have been implicated in several C-X bond forming reactions and have been demonstrated to activate non-polar substrates. Thus, in order to advance the understanding of these reactive systems and to exploit the prospects for synthetic applications toward small molecule transformations, further study is warranted. Presented herein is the study of (IPr)Cu(NR2), (IPr)Cu(OR) and (IPr)Cu(SR) {IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene} complexes in the catalytic hydroamination of electron-deficient olefins toward regioselective formation of C-N, C-O and C-S bonds. The substrate scope encompasses alkyl and aryl amines, including primary and secondary variants, as well as alcohols and thiols. Olefins with cyano, acyl, and ester functionalities and vinylarenes are reactive. In a demonstration of potential application, the hydroamination of p-nitrostyrene with N-methylbenzylamine by (IPr)Cu(NHPh) provides a straight-forward single-step route to an anti-arrhythmic agent. Mechanistic studies are consistent with a reaction pathway that involves intermolecular nucleophilic addition of the Cu-amido to free olefin. In an effort to obtain more active catalyst systems that.