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Synthesis Spectroscopic Characterization And Reactivity Of The High Valent Metal Oxo Imido Cores Of The Late Transition Metals
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Book Synopsis Synthesis, Spectroscopic Characterization and Reactivity of the High-valent Metal-oxo/imido Cores of the Late Transition Metals by : Subrata Kundu
Download or read book Synthesis, Spectroscopic Characterization and Reactivity of the High-valent Metal-oxo/imido Cores of the Late Transition Metals written by Subrata Kundu and published by . This book was released on 2013 with total page 225 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Book Synopsis The Synthesis, Characterization and Reactivity of Novel Late-transition Metal Bridging Amido and Imido Complexes by : Manoj K. Kolel-Veetil
Download or read book The Synthesis, Characterization and Reactivity of Novel Late-transition Metal Bridging Amido and Imido Complexes written by Manoj K. Kolel-Veetil and published by . This book was released on 1995 with total page 470 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Book Synopsis Synthesis, Characterization and Reactivity Studies of Low-coordinate Late Transition Metal Complexes and the Preparation and Characterization of a Low-coordinate Samarium Complex by : Pei Zhao
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.
Book Synopsis Late Transition Metal Oxo and Imido Complexes by :
Download or read book Late Transition Metal Oxo and Imido Complexes written by and published by . This book was released on 1992 with total page 4 pages. Available in PDF, EPUB and Kindle. Book excerpt: A range of new phosphine Au(I) oxo complexes, [(LAu)[sub 3]([mu]-O)][sup +], were prepared, testing the limits of the phosphine steric and electronic properties. Their reaction with reducing agents (hydrazines, CO and RNC) give a variety of new and known gold clusters in unprecedented high yields and establish the steric and electronic relationships between the phosphine and the nuclearity of the product Au cluster. The [L[sub 2]Pt([mu]-O)][sub 2] class of dioxo complexes has been expanded to include the first anionic oxo complex, ([(dppm-H)Pt([mu]-O)][sub 2])Li[sub 2] and the first Pt imido complexes, [(L[sub 2]Pt)[sub 2]([mu]-O)([mu]-NR)] and [L[sub 2]Pt([mu]-NR)][sub 2]. The previously observed Rh imido/amido A-frame chemistry has been extended to Ir. The p-MePh-imido complex has been characterized by X-ray diffraction and clearly shows the resonance delocalization of the nitrogen lone pair into the aryl ring which is responsible for the previously observed electrophilic ring addition and oxidative ring coupling reactions.
Book Synopsis Formation and Reactivity of High Valent Metal-oxo Species by :
Download or read book Formation and Reactivity of High Valent Metal-oxo Species written by and published by . This book was released on 2006 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt:
Book Synopsis Synthesis, Reactivity and Mechanistic Studies on Oxo, Imido and Alkylidine Complexes of the Early Transition Metals by : Jonathan Paul Mitchell
Download or read book Synthesis, Reactivity and Mechanistic Studies on Oxo, Imido and Alkylidine Complexes of the Early Transition Metals written by Jonathan Paul Mitchell and published by . This book was released on 1992 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt:
Book Synopsis Synthesis, reactivity and mechanistic studies on oxo, imido and alkylidene complexes of the early transition metals by : Jonathan Paul Mitchell
Download or read book Synthesis, reactivity and mechanistic studies on oxo, imido and alkylidene complexes of the early transition metals written by Jonathan Paul Mitchell and published by . This book was released on 1992 with total page 0 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Book Synopsis Late Transition Metal Oxo and Imido Complexes. Progress Report, May 15 1992--May 14, 1992 by :
Download or read book Late Transition Metal Oxo and Imido Complexes. Progress Report, May 15 1992--May 14, 1992 written by and published by . This book was released on 1992 with total page 4 pages. Available in PDF, EPUB and Kindle. Book excerpt: A range of new phosphine Au(I) oxo complexes, [(LAu)3([mu]-O)], were prepared, testing the limits of the phosphine steric and electronic properties. Their reaction with reducing agents (hydrazines, CO and RNC) give a variety of new and known gold clusters in unprecedented high yields and establish the steric and electronic relationships between the phosphine and the nuclearity of the product Au cluster. The [L2Pt([mu]-O)]2 class of dioxo complexes has been expanded to include the first anionic oxo complex, ([(dppm-H)Pt([mu]-O)]2)Li2 and the first Pt imido complexes, [(L2Pt)2([mu]-O)([mu]-NR)] and [L2Pt([mu]-NR)]2. The previously observed Rh imido/amido A-frame chemistry has been extended to Ir. The p-MePh-imido complex has been characterized by X-ray diffraction and clearly shows the resonance delocalization of the nitrogen lone pair into the aryl ring which is responsible for the previously observed electrophilic ring addition and oxidative ring coupling reactions.
Book Synopsis Preparation, Characterisation and Reactivity of Low Oxidation State d-Block Metal Complexes Stabilised by Extremely Bulky Amide Ligands by : Jamie Hicks
Download or read book Preparation, Characterisation and Reactivity of Low Oxidation State d-Block Metal Complexes Stabilised by Extremely Bulky Amide Ligands written by Jamie Hicks and published by Springer. This book was released on 2016-11-02 with total page 0 pages. Available in PDF, EPUB and Kindle. Book excerpt: This thesis describes the synthesis and characterization of numerous metal-metal bonded complexes that are stabilized by extremely bulky amide ligands. It provides a comprehensive overview of the field, including discussions on groundbreaking complexes and reactions, before presenting in detail, exciting new findings from the PhD studies. The thesis appeals to researchers, professors and chemistry undergraduates with an interest in inorganic and/or organometallic chemistry.
Book Synopsis Syntheses, Characterization, Electrochemistry and Photochemical Properties of Some High-Valent Oxo and Imido Complexes of Osmium and Rhenium by : 鄭郁棋
Download or read book Syntheses, Characterization, Electrochemistry and Photochemical Properties of Some High-Valent Oxo and Imido Complexes of Osmium and Rhenium written by 鄭郁棋 and published by . This book was released on 2017-01-27 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt:
Book Synopsis Ground and Excited State Spectroscopic Studies of High Valent Metal-oxo Catalytic Intermediates by : Robert Michael Jones
Download or read book Ground and Excited State Spectroscopic Studies of High Valent Metal-oxo Catalytic Intermediates written by Robert Michael Jones and published by . This book was released on 1998 with total page 650 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Book Synopsis Synthesis, Characterization and Reactivity of Some Low-coordinate, Low-oxidation State Heavier Main Group 14 Element Species by : Madison Louis McCrea-Hendrick
Download or read book Synthesis, Characterization and Reactivity of Some Low-coordinate, Low-oxidation State Heavier Main Group 14 Element Species written by Madison Louis McCrea-Hendrick and published by . This book was released on 2018 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt: This dissertation describes the synthesis, characterization and reactivity of some low-coordinate, low-oxidation state heavier main group 13 and 14 element species. Chapter 2 describes the reactivity of the heavier main group 13 element digallene, (GaAr[superscript iPr4])2, (Ar[superscript iPr4] = -C6H3-2,6-(C6H3-2,6-[superscript i]Pr2)2) with group 6 transition metal hexacarbonyls under photoirradiation to form the bis(gallanediyl) complexes, trans-bis(GaAr[superscript iPr4])2M(CO)4 (M = Cr, Mo, or W). The mechanism of formation of these products was investigated both computationally and experimentally. A postulated intermediate in their formation is the monogallanediyl complex, Ga(Ar[superscript iPr4])Mo(CO)5 which was synthesized by the reaction (GaAr[superscript iPr4])2 with two equivalents Mo(CO)5NMe3. (GaAr[superscript iPr4])2 was also reacted at 25°C with Co2(CO)8 to give Ga(Ar[superscript iPr4])Co2(CO)7, in which the gallanediyl fragment is bound to each cobalt atom in a bridging fashion. Chapter 3 is an extension of the work in Chapter 2 to the reactions of the heavier main group 14 element dimetallynes, (EAr[superscript iPr4])2 (E = Ge or Sn), with group 6 transition metal hexacarbonyls under photoirradiative conditions. These reactions afforded the products {Ar[superscript iPr4]EM(CO)4}2 (E = Ge or Sn; M = Cr, Mo, or W) which featured rhomboid E2M2 cores with Ar[superscript iPr4]E units bridging transition metal tetracarbonyl fragments, M(CO)4. Chapter 4 describes the reactions of the aryl tin(II) hydrides {Ar[superscript iPr6]Sn([mu]-H)}2 (Ar[superscript iPr6] = C6H3-2,6-(C6H2-2,4,6-[superscript i]Pr6)2) and {Ar[superscript iPr4]Sn([mu]-H)}2 with phenyl acetylene and diphenyl acetylene. The reactions with diphenyl acetylene affords simple insertion of the Sn-H bond into a [pi]-bond of the alkyne to yield the products ArSnC(Ph)C(H)Ph (Ar = Ar[superscript iPr6] or Ar[superscript iPr4]). In contrast, the reaction of {ArSn([mu]-H)}2 with phenyl acetylene affords different products that are connected with the presence (Ar[superscript iPr6]) or absence (Ar[superscript iPr4]) of an isopropyl group at the remote para position of the flanking aryl rings of the terphenyl substituent. When {Ar[superscript iPr6]Sn([mu]-H)}2 is reacted with phenyl acetylene the product Ar[superscript iPr6](H)SnC(H)C(Ph)Sn(H)Ar[superscript iPr6] containing a 1,2-distannacyclobut-3-ene moiety is obtained as a colorless solid. In contrast, the reaction of {Ar[superscript iPr4]Sn([mu]-H)}2 with phenyl acetylene affords a red product of formula Ar[superscript iPr4]SnC(H)C(Ph)Sn(H)2Ar[superscript iPr4] with the tin atoms having different oxidation states of +2 and +4 as determined by solution 119Sn NMR spectroscopy. Chapter 5 describes the synthesis and characterization of the most sterically congested tetrylenes currently known: E(Ar[superscript iPr6])2 (E = Ge, Sn, or Pb). Computational studies of these tetrylenes and E(Ar[superscript Me6])2 (Ar[superscript Me6] = C6H3-2,6-(C6H2-2,4,6-Me3)2) and E(Ar[superscript iPr4])2 were also performed with and without dispersion corrections to evaluate the contribution of London dispersion force effects on the C[subscript ipso]-E-C[subscript ipso] interligand angle.
Book Synopsis Synthesis and Reactivity of Early Transition Metal Complexes by : LeGrande Mancel Slaughter (III)
Download or read book Synthesis and Reactivity of Early Transition Metal Complexes written by LeGrande Mancel Slaughter (III) and published by . This book was released on 2000 with total page 416 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Book Synopsis Oxo Complexes of Tungstenocene Via Oxidation of (W(Eta(5)-C5H5)2(OCH3) (CH3)) and Related Reactions: Synthesis, Structural Characterization, and Photodisproportionation of the Spin Paired D(1)-d(1) Oxo Bridged Dimer ((W(Eta(5)-C5H5)2(CH3))2(Mu-O))2(+) and Synthesis and Charaterization of the D(0) Terminal Oxo Complex (W(Eta(5)-C5H5)2(O)(CH3))(+). by :
Download or read book Oxo Complexes of Tungstenocene Via Oxidation of (W(Eta(5)-C5H5)2(OCH3) (CH3)) and Related Reactions: Synthesis, Structural Characterization, and Photodisproportionation of the Spin Paired D(1)-d(1) Oxo Bridged Dimer ((W(Eta(5)-C5H5)2(CH3))2(Mu-O))2(+) and Synthesis and Charaterization of the D(0) Terminal Oxo Complex (W(Eta(5)-C5H5)2(O)(CH3))(+). written by and published by . This book was released on 1993 with total page 52 pages. Available in PDF, EPUB and Kindle. Book excerpt: There has been remarkable growth throughout the 1980s in the chemistry of transition metal oxo complexes. Interest in what had been regarded as a mature area was rekindled in part by the recognition of the role of the oxo functionality as a 'spectator' ligand in catalytic alkene metathesis, and has been fueled by developments in the chemistry of transition metal porphyrin oxo complexes (including their roles in hydrocarbon oxidations and in alkene epoxidation and hydroxylation reactions), by continuing rapid evolution of our understanding of biologically relevent oxo transfer reactions, by extraordinary advances in the use of oxo complexes as catalysts for alkene hydroxylation and epoxidation, and most recently, by the remarkable catalystic activity demonstrated by high valent rehenium oxo alkyls. These development have been paralleled by significant advances in the syntheses of oxo complexes, including the preparations of 'low valent' oxo complexes and of high valent oxo alkyl complexes, and marked extentions of the rational synthesis of organometallic oxo complexes.
Book Synopsis The Synthesis and Characterization of Early High-late Low Oxidation State Mixed Metal Organometallic Compounds by :
Download or read book The Synthesis and Characterization of Early High-late Low Oxidation State Mixed Metal Organometallic Compounds written by and published by . This book was released on 1999 with total page pages. Available in PDF, EPUB and Kindle. Book excerpt:
Book Synopsis New Late Transition Metal Oxo and Hydrazido Complexes by : Hui Shan
Download or read book New Late Transition Metal Oxo and Hydrazido Complexes written by Hui Shan and published by . This book was released on 1998 with total page 412 pages. Available in PDF, EPUB and Kindle. Book excerpt: Rhodium/gold (1a, 1b) and iridium/gold (2) [mu] 4 -oxo complexes with diene ligands have been synthesized from reactions between [(AuPPh 3) 3 ([mu]-O)]BF 4 and [(diene)MCl] 2 (M = Rh, diene = NBD, COD; M = Ir, diene = COD). A family of platinum/gold [mu] 3 -oxo complexes with COD ligand (3a-3g), [(1,5-COD)Pt([mu]-OAuL)] 2 (BF 4) 2 (L = PPh 3, PPh 2 Pr i, PPh 2 Et, P(o-toly) 3, P(p-toly) 3, P(p-MeOPh) 3, P(p-CF 3 Ph) 3), and a gold free platinum [mu] 3 -oxo/hydroxo complex, [(1,5-COD) 4 Pt 4 ([mu] 3 -O) 2 ([mu]-OH)](BF 4) 3 (5) are also prepared from the novel oxo/halide exchange synthetic route. The structural and chemical properties of these new compounds have been studied. One of the special properties of 5 is its unique ability of reacting with unactivated olefins (e.g. ethylene, tetramethylethylene, and cyclooctadiene) to give oxidized organic products or intermediate adducts. The mechanism of olefin insertion into M-O bond is favored in the attempted rationalization of the formation of the diverse products observed in the reactions. A whole family of complexes (13a-13f), [(AuL) 6 N 2](BF 4) 2 (L = PPh 2 Pr i, PPh 2 Et, PPh 2 Me, P(p-toly) 3, P(p-MeOPh) 3, P(p-CF 3 Ph) 3), which contains dinitrogen bonding simultaneously to six metal atoms is synthesized and characterized. These compounds are studied as structural models for the coordination of dinitrogen at the center of the nitrogenase Fe-Mo cofactor cluster. The existence of our compound supports the idea that the bond order of dinitrogen is reduced from 3 to 1 on initial coordination to the inside of the cluster. The chemical properties of these new hydrazido complexes have been studied. One of the special properties of 13 is their unique ability of being reduced and protonated to generate ammonia. This reactivity makes them suitable chemical model for the reduction of dinitrogen at the active site of nitrogenase. Considerable experimental work has been devoted to the understanding of the protonation process of complex 13a, [(AuPPh 2 Pr i) 6 N 2](BF 4) 2 . Two partially protonated species, [(AuPPh 2 Pr i) 5 HN 2] 2+ and [(AuPPh 2 Pr i) 4 H 2 N 2] 2+, are determined and considered to be key intermediates in the generation of ammonia. Preliminary kinetic studies have been carried out, which led to the proposal that the formation of [(AuPPh 2 Pr i) 5 HN 2] 2+ species occur through an associate process involving the formation of a highly reactive hyper-coordinated complex, [(AuPPr i Ph 2) 6 N 2 H] 3+ [double dagger], in the transition-state.
Book Synopsis Syntheses, Characterization, Electrochemistry and Photochemical Properties of Some High-valent Oxo and Imido Complexes of Osmium and Rhenium by : Yuk-ki Cheng
Download or read book Syntheses, Characterization, Electrochemistry and Photochemical Properties of Some High-valent Oxo and Imido Complexes of Osmium and Rhenium written by Yuk-ki Cheng and published by . This book was released on 1997 with total page 444 pages. Available in PDF, EPUB and Kindle. Book excerpt:
