Relevant bibliographies by topics / Transition metals – Reactivity

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  2. Dissertations / Theses
  3. Books
  4. Book chapters
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Academic literature on the topic 'Transition metals – Reactivity'

Author: Grafiati
Published: 4 June 2021
Last updated: 12 February 2022

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Journal articles on the topic "Transition metals – Reactivity"

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Catalán, Silvia, Sócrates B. Munoz, and Santos Fustero. "Unique Reactivity of Fluorinated Molecules with Transition Metals." CHIMIA International Journal for Chemistry 68, no. 6 (2014): 382–409. http://dx.doi.org/10.2533/chimia.2014.382.

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Sieklucka, Barbara. "REACTIVITY AND PHOTOREACTIVITY OF CYANOCOMPLEXES OF THE TRANSITION METALS." Progress in Reaction Kinetics and Mechanism 24, no. 3 (1999): 165–221. http://dx.doi.org/10.3184/007967499103165085.

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Trinh, Quang Thang, Bhadravathi Krishnamurthy Chethana, and Samir H. Mushrif. "Adsorption and Reactivity of Cellulosic Aldoses on Transition Metals." Journal of Physical Chemistry C 119, no. 30 (2015): 17137–45. http://dx.doi.org/10.1021/acs.jpcc.5b03534.

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Kobayashi, Katsuaki, and Koji Tanaka. "Reactivity of CO2 Activated on Transition Metals and Sulfur Ligands." Inorganic Chemistry 54, no. 11 (2015): 5085–95. http://dx.doi.org/10.1021/ic502745u.

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Sugiishi, Tsuyuka, and Hiroyuki Nakamura. "Reactivity of Propargylic Amines in the Presence of Transition Metals." Journal of Synthetic Organic Chemistry, Japan 72, no. 6 (2014): 654–65. http://dx.doi.org/10.5059/yukigoseikyokaishi.72.654.

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Catalan, Silvia, Socrates B. Munoz, and Santos Fustero. "ChemInform Abstract: Unique Reactivity of Fluorinated Molecules with Transition Metals." ChemInform 46, no. 7 (2015): no. http://dx.doi.org/10.1002/chin.201507331.

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Yanada, Kazuo, Hiromi Yamaguchi, Reiko Yanada, Haruo Meguri, and Shuji Uchida. "Modifying Effect of Selenium on Catalytic Reactivity of Transition Metals." Chemistry Letters 18, no. 6 (1989): 951–54. http://dx.doi.org/10.1246/cl.1989.951.

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Kočovský, Pavel. "Organic Reactivity Control by Means of Neighboring Groups and Organometallics. A Personal Account." Collection of Czechoslovak Chemical Communications 59, no. 1 (1994): 1–74. http://dx.doi.org/10.1135/cccc19940001.

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This review summarizes the main topics of our research and covers the period of the last 15 years. The prime interest is focused on various ways of controlling the regio- and stereoselectivity of selected organic reactions, in particular electrophilic additions, cleavage of cyclopropane rings, and allylic substitutions by means of neighboring groups and/or transition and non-transition metals. In the first part, the factors governing the course of electrophilic additions are assessed, culminating in the formulation of selection rules for the reactivity of cyclohexene systems, and in a concise synthesis of the natural cardioactive drug, strophanthidin. These studies also contribute to a better understanding of the mechanisms of electrophilic additions. The second part describes recent developments in the stereo- and regiocontrolled cleavage of cyclopropane rings by non-transition metals (Tl and Hg), and the reactivity and transmetalation (with Pd) of the primary products. This methodology has resulted in novel routes to unique polycyclic structures, and will have synthetic applications in the near future. Evidence for the stereospecific "corner" cleavage of the cyclopropane ring has been provided for the first time for Tl and later for Hg. The third part deals with transition metal-catalyzed allylic substitution. Evidence for a new "syn" mechanism for the formation of the intermediate (π-allyl)palladium complex has been provided, which runs counter to the generally accepted "anti" mechanism. A novel method for a Pd-catalyzed allylic oxidation has been developed and employed in the synthesis of natural sesquiterpenes. The increasing importance of transition and non-transition metals for synthetic organic chemistry is demonstrated by their unique reactivity in a number of the papers included in this review.
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Guo, Xue, Li, et al. "Effects of Transition Metal Substituents on Interfacial and Electronic Structure of CH3NH3PbI3/TiO2 Interface: A First-Principles Comparative Study." Nanomaterials 9, no. 7 (2019): 966. http://dx.doi.org/10.3390/nano9070966.

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To evaluate the influence of transition metal substituents on the characteristics of CH3NH3PbI3/TiO2, we investigated the geometrical and electronic properties of transition metal-substituted CH3NH3PbI3/TiO2 by first-principles calculations. The results suggested that the substitution of Ti4+ at the five-fold coordinated (Ti5c) sites by transition metals is energetically favored. The substituted interface has enhanced visible light sensitivity and photoelectrocatalytic activity by reducing the transition energies. The transition metal substitution can effectively tune the band gap of the interface, which significantly improves the photo-reactivity. The substituted systems are expected to be more efficient in separating the photo-generated electrons-holes and active in the visible spectrum.
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Davison, Allan J., Qizhuan Wu, Jim Moon, and Arnold Stern. "Among a range of transition metals and ligands vanadium∙desferroxamine excels in accelerating reactivity of ferrocytochrome c toward molecular oxygen." Biochemistry and Cell Biology 72, no. 5-6 (1994): 169–74. http://dx.doi.org/10.1139/o94-025.

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Despite early knowledge of the requirement for metals in the reactions of ferrocytochrome c with oxygen, the relative effectiveness of metals and the factors that modulate effectiveness remain unknown. We have compared the catalytic power of five metals and report the effects of pH and ligand on their effectiveness as catalysts. Catalysis by metal ions was greatest at higher pH, where the rate of aerobic oxidation was lowest. Iron (Fe2+), copper (Cu2+), vanadium(V) (V(V)), manganese (Mn2+), and aluminum (Al3+) were tested in combination with EDTA, ADP, histidine, or desferrioxamine (Des) at pH 2.6, 3.2, and 4.0. At pH 2.6, only vanadium(V) increased the initial rate of the oxidation of ferrocytochrome c (by 6.2-fold). At pH 4.0, however, all the metals markedly stimulated the oxidation of cytochrome c. The order of effectiveness was V(V)∙Des >> Cu∙ADP2+ > Fe∙EDTA2+ > Mn∙Des2+ > Al∙EDTA3+ (where the stated ligand represents the most stimulating one for a given metal). At pH 3.2 the metal complexes had intermediate effects, with vanadium again being the most effective. The preeminence of vanadium among the metals is novel. Where the heme crevice is closed (pH 4), transition metal ions mediated almost all of the reduction of oxygen, while at the lowest pH (2.6) transition metal ions were largely unnecessary. Vanadium(V) was the most active of the metals at all values of pH and the only metal to accelerate the oxidation of ferrocytochrome c at pH 2.6. Understanding of the range of biological actions of vanadium will not be complete without a knowledge of its redox reactivity within the components of biological systems.Key words: aerobic oxidation, ferrocytochrome c, transition metals, ligands, vanadium, iron, manganese, copper, aluminium.
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Dissertations / Theses on the topic "Transition metals – Reactivity"

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Rossin, Joseph A. "Synthesis, characterization and reactivity of transition metal containing zeolites." Diss., Virginia Polytechnic Institute and State University, 1986. http://hdl.handle.net/10919/76271.

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Transition metal containing zeolites (zeolite A and ZSM-5) were prepared by addition of various transition metal containing substrates to zeolite synthesis gels. Crystal growth data were recorded in order to determine the influence of the transition metal species on the rate of crystal growth. X-ray diffraction, oxygen adsorption, FTIR and SEM were utilized to evaluate crystal purity. X-ray photoelectron spectroscopy (XPS), chemical analysis and electron microprobe analysis were performed in order to ascertain the position (intrazeolitic versus surface) and homogeneity of the transition metal. It was concluded that intrazeolitic transition metals were produced by the novel procedure presented in this work. 1-Hexene hydroformylation by rhodium zeolite A showed intrazeolitic rhodium to migrate to the external surface of the zeolite. However, in the presence of a solution and surface rhodium poison, intrazeolitic rhodium was found to hydroformylate 1-hexene exclusively to heptanal. Ruthenium containing zeolite A was evaluated under CO-hydrogenation conditions. No migration of intrazeolitic ruthenium to the external surface of the zeolite was observed over the course of the reaction. The product distribution obtained for this catalyst did not follow a log normal behavior. Also, loss of zeolite crystallinity was observed following the reaction. Cobalt ZSM-5 was evaluated under CO-hydrogenation conditions. No migration of cobalt to the external surface of the zeolite occurred. XPS analysis of the catalyst following various stages of the reaction indicated that intrazeolitic cobalt was not reduced to the zero valent state. Consequently, the non-zero valent cobalt was not capable of hydrogenating carbon monoxide.<br>Ph. D.
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Haslam, Claire Elizabeth. "Organometallic mechanisms and reactivity : towards new catalysts for polyketones." Thesis, University of Sheffield, 1999. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.310787.

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MUDARMAH, KHALIL. "REACTIVITY OF MOLYBDENUM AND TUNGSTEN SULFIDO COMPLEXESWITH FIRST-SERIES TRANSITION METALS." Cleveland State University / OhioLINK, 2019. http://rave.ohiolink.edu/etdc/view?acc_num=csu1566563467202265.

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Radulović, Stojan. "Solvation, reactivity and spectroscopy of complexes of some first row transition metals." Thesis, University of Leicester, 1988. http://hdl.handle.net/2381/27867.

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The work in this thesis is mainly concerned with the discussion of effect of solvation on the reaction kinetics of inorganic complexes. Rate constants for chemical reactions in various aqueous cosolvent systems have been measured and analysed. Crystal structure of several Fe (II) complexes are analysed from crystallographic data for possible structural parameters which might have effect on solvation. Solubility data, for a range of inorganic salts containing simple and complex ions, are reported for aqueous solutions and for solutions in aqueous cosolvent mixtures. Transfer chemical potentials for single ions in aqueous i-PrOH and t-BuOH solvent mixtures are determined using solubility data for salts in conjunction with TATB, tetraphenylarsonium tetraphenylboranate, assumption and are compared with those in corresponding aqueous methanol, ethanol and acetone solvent mixtures. Kinetic data are reported for reaction between [Fe (gmi)3]²+ and hydroxide ions at atmospheric and elevated pressures in above binary aqueous mixtures. Initial state and transition state analysis of reactivity trends for hydroxide attack on other Fe (II) diimine complexes in aqueous methanol solvent mixtures are reported. Dependence of visible absorption spectra on solvent has been examined for a number of Fe (II) and Fe (III) mixed ligand complexes. Preliminary redox study of the of Fe (II) and Fe (III) complexes is also reported.
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Mapolie, Selwyn Frank. "The synthesis and reactivity of binuclear μ-hydrocarbyl complexes of some transition metals". Doctoral thesis, University of Cape Town, 1988. http://hdl.handle.net/11427/22208.

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The new μ-(l,n)-alkanediyl compounds [(ƞ⁵-C₅R₄Me)Fe(CO)₂ ]₂{μ-(CH₂)n}, (R = H, n = 3 -10 and R =Me, n =3 - 6), [Mn(CO)₅]₂{μ-(CH₂)n} (M = Mn, n = 4-6 and M = Re, n= 3 and 4) have been prepared using essentially two synthetic routes. Thus the iron compounds were synthesized by the reaction of Na[(ƞ⁵-C₅R₄Me)Fe(CO)₂ ] with the appropriate dibromoalkane. The manganese and rhenium compounds on the other hand, were prepared by the decarbonylation of the corresponding diacyl compounds of the type, [M(CO)₅]₂{μ-CO(CH₂)nCO} (M = Mn or Re). These diacyl species in turn were synthesized by the reaction of Na[M(CO)s] with diacyl chlorides. All the new compounds have been fully characterized by microanalysis, infrared, ¹H and ¹³C nmr spectroscopy. The mass spectra of the compounds have been investigated and the fragmentation patterns are discussed and compared with other known polymethylene compounds. An extensive investigation into the reactivity of the new alkanediyl compounds has been carried out. Thus for example the reactivity of the compounds [CpFe(CO)₂]₂{μ-(CH₂)n} with nucleophiles such as tertiary phosphines and isocyanides, yield diacyl compounds of the type [CpFe(CO)L]₂{μ-CO(CH₂)nCO} (Cp = C₅H₄Me or C₅Me₅) and (L = tertiary phosphine or isocyanide). Similar ligand induced CO insertion reactions were observed for the manganese and rhenium alkanediyl compounds. The products from these reactions were characterized using the analytical techniques mentioned earlier. The reactions are discussed and compared with those of mononuclear alkyl compounds of manganese, rhenium and iron. The reactions of some polymethylene bridged compounds with synthesis gas have also been investigated. This reaction is of importance in view of the fact that polymethylene bridged compounds have been implicated in a number of catalytic processes e.g the Fischer- Tropsch reaction. The reaction with synthesis gas was found to yield bifunctional alcohols of the type HO(CH₂)nOH. In a separate study, the binuclear μ-phthaloyl compounds of manganese, rhenium,iron,molybdenum,cobalt and rhodium were prepared and characterized. The phthaloyl compounds of manganese, rhenium and iron were decarbonylated to form the corresponding μ-phenylene compounds. The reactions of some of these compounds with nucleophiles and electrophiles have been studied and the results compared with that of the corresponding mononuclear benzoyl and phenyl compounds.
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Shaw, Alan. "Synthesis and reactivity studies on oxo and sulphide compounds of the early transition metals." Thesis, Durham University, 1989. http://etheses.dur.ac.uk/6554/.

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This thesis describes studies directed towards the preparation of new oxo compounds of the early transition metals with a view to delineating some of the complex factors which govern their stability and reactivity. For a number of the types of compound studied, the work has also been extended to analogous sulphide systems in order to provide a contrast with another chalcogenide element and further aid an understanding of the bonding and reactivity of both of these elements in a transition metal enviroment. Chapter 1 highlights the areas of transition metal oxo chemistry of relevance to the general theme of the thesis. Chapter 2 describes the use of the commercially available reagents Me(_3)SiYR (R = alkyl, SiMe(_3); Y = O, S), for rapid, convenient, solution syntheses of transition metal oxohalide and sulphidohalide compounds of molybdenum, tungsten, niobium and tantalum. In addition, this methodology allows the preparation of mixed oxosulphidohalide materials and, in certain cases, intermediate alkoxo(siloxo) halide compounds have been isolated. Chapter 3 describes the synthesis, characterisation and reactivity of a series of mononuclear mono-oxo complexes of molybdenum and tungsten including M(O)(OAr)(_4) [M=W, Ar=2,6-Me(_2)C(_6)H(_3) (DMP), 2,4,6-Me(_3)C(_6)H(_2) (TMP), 2,6-Pr(^i)C(_6)H(_3) (DIPP); M=Mo, Ar=(DMP)], M(_2)(O)(_3)(DMP)(_6) and Mo(O)C1(_2)(DMP)(_2). Attempts to synthesise related mononuclear complexes containing the cis di-oxo moeity are also discussed. Chapter 4 describes the synthesis and reactivity of seven coordinate oxo and sulphidohalide derivatives of niobium and tantalum which exhibit the phenomenon of bond-stretch isomerism. Compounds prepared include Nb(O)Br(_3)(PMe(_3))(_3), Nb(S)X(_3)(PMe(_3))(_3) (X=C1, Br) and Ta(S)C1(_3)(PMe(_3))(_3). The latter three have been characterised by X-ray crystallography. Chapter 5 describes the synthesis and reactivity of half-sandwich oxo compounds of niobium and tantalum. Some of the derivatives prepared include[CpNbC1(_3)](_2)(µ(_2)-O), [CpTaC1(_3)](_2)(|µ(_2)-O) and [Cp*TaC1(_3)](_2)(µ(_2)O). The stability of [Cp*Ta(O)Cl(_2)](_2) has been investigated and the X-ray structure of the trinuclear decomposition product Cp*(_3)Ta(_3)O(_4)C1(_4) is described. Chapter 6 describes the use of alkali metal aryloxides as intercalating agents and the preparation of a series of novel intercalation compounds, of the type W(O)(_2)C1(_2)xM (M = Li, Na and K) which display the properties characteristic of tungsten bronzes. Chapter 7 gives experimental details for chapters 2 6.
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Knopf, Ioana. "Carbon dioxide utilization : from fundamental reactivity to catalysis using transition metals supported by macrocyclic diphosphines." Thesis, Massachusetts Institute of Technology, 2017. http://hdl.handle.net/1721.1/112359.

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Thesis: Ph. D., Massachusetts Institute of Technology, Department of Chemistry, 2017.<br>This electronic version was submitted by the student author. The certified thesis is available in the Institute Archives and Special Collections.<br>Cataloged from student-submitted PDF version of thesis. Page 308 blank.<br>Includes bibliographical references.<br>Molybdate, a molecular metal oxide, readily binds CO₂ at room temperature to produce a robust monocarbonate complex, [MoO₃(k²-CO₃)]²-. In the presence of excess CO₂, a pseudo-octahedral dioxo dicarbonate complex, [MoO₃(k²-CO₃)₂]²-, is formed. The monocarbonate [MoO₃(k²-CO₃)]²- reacts with triethylsilane to produce formate together with silylated molybdate. A different system investigated in the context of CO₂ reduction to formate was sodium borohydride. The uptake of three equivalents of CO₂ by NaBH₄ is described, along with full spectroscopic and crystallographic characterization of the resulting triformatoborohydride, Na[HB(OCHO)₃]. In order to develop catalytic transformations for CO₂ utilization, we undertook an extensive investigation into the synthesis of novel phosphine ligand architectures that could support transition metal catalysts. A new, chelating, cationic P,N-ligand, [pyP₂dmb₂][SbF₆], was synthesized by treatment of the robust bicyclic diphosphane, 3,4,8,9-tetramethyl-1,6-diphosphabicyclo(4.4.0)deca-3,8-diene or P₂dmb₂, with 2-iodopyridine, followed by an anion exchange. This phosphino-phosphonium salt was investigated as a ligand for group 6 and group 10 transition metals. Other cationic and zwitterionic ligand frameworks were also briefly investigated. A family of cis-macrocyclic diphosphines was prepared in just three steps from white phosphorus and commercial materials using a modular synthetic approach. Alkylation of bicyclic diphosphane P₂dmb₂ produced phosphino-phosphonium salts [RP₂dmb₂]X, where R is methyl, benzyl, isobutyl, or neopentyl. Treatment of these salts with organometallic reagents yielded macrocyclic diphosphines of the form cis-1-R-6-R2-3,4,8,9-tetramethyl-2,5,7,10-tetrahydro-1,6-DiPhospheCine, or R,R2-DPC, in which R2 is methyl, cyclohexyl, phenyl, mesityl or neopentyl. Alternatively, symmetric diphosphine Cy₂-DPC was synthesized from the dichlorodiphosphine Cl₂P₂dmb₂. Multidentate ligands with additional S, P and N donor atoms have also been prepared. The coordination chemistry of these cis-macrocyclic diphosphines was explored, with a focus on nickel and cobalt complexes. An unusual iodide-bridged cobalt(I) dimer, [(Cy₂-DPC)CoI]₂, was prepared and structurally characterized. These nickel and cobalt complexes supported by cismacrocyclic diphosphines were investigated as potential catalysts for the coupling of carbon dioxide and ethylene to produce acrylate, a valuable polymer precursor. The nickel complexes studied showed similar or better turnover numbers for acrylate production compared to complexes of commercial diphosphine ligands. Although not yet catalytic, the first examples of cobalt complexes capable of mediating acrylate formation from CO₂ and ethylene are reported.<br>by Ioana Knopf.<br>Ph. D.
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Sazama, Graham Thomas. "Late First-Row Transition Metals in Weak Ligand Fields - Correlating High-Spin Electronic Structure and Reactivity." Thesis, Harvard University, 2013. http://dissertations.umi.com/gsas.harvard:11012.

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High spin has been shown to be necessary for optimal reactivity of transition metal complexes toward the activation and functionalization of C-H bonds. This thesis presents our examination of the weak-field, tripodal, trianionic tris(pyrrolyl)ethane (tpe) ligand and its complexes. Outer-sphere oxidation of the manganese, iron, cobalt, nickel and zinc complexes of tpe were performed by electrochemical and chemical methods. Electrochemical oxidation occurred at the same potential for each species, suggesting a ligand-based oxidation. The reaction product of chemical oxidation of iron showed oxidation of a pyrrole unit followed by H-atom abstraction to form a dichelated species. Density functional theory calculations confirm these results, and in silico oxidation of the complexes is entirely ligand-based. These results establish that tpe complexes are oxidized at the pyrrolide subunits in outersphere electron transfers, and elucidate minimal metal-ligand electronic communication. The more reactive \([(tpe)Fe(THF)]^−\) anion exhibits rapid binding of three equivalents of tert-butyl isonitrile, while reaction with excess carbon monoxide induces ligand fragmentation to form a species wherein two molecules of carbon monoxide have been reductively coupled. A mechanism based on the observed isonitrile species is proposed. The use of inner-sphere oxidant reagents allows for several stable iron (III) complexes of tpe to be isolated and characterized. Alkyl peroxides and alkyl disulfides, organic azides, and diphenyldiazomethane are all shown to oxidize iron by a single electron. Reaction with organic azides results in the formation of iron (III) amide species, likely as a result of Hatom abstraction. The weak-field of tpe creates a high propensity for forming high-spin iron (III) complexes, to the extent that diphenyldiazoalkane acts as a redox-active ligand and provides a one-electron reservoir to reveal a high-spin \(Fe^{3+}\). Spectroscopic and computational studies were undertaken to rigorously assign the physical oxidation state of iron in all cases. Given the outer-sphere redox liability of the tpe ligand, and the capability for inner-sphere oxidation local to iron, tpe complexes of iron represent a new class of metal-ligand redox activity, wherein the metal and ligand form two separate redox reservoirs, accessible via different mechanisms.<br>Chemistry and Chemical Biology
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Mitchell, Jonathan Paul. "Synthesis, reactivity and mechanistic studies on oxo, imido and alkylidene complexes of the early transition metals." Thesis, Durham University, 1992. http://etheses.dur.ac.uk/5788/.

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This thesis describes studies directed towards the synthesis and reactivity of transition metal species containing multiply bonded oxo, imido and alkylidene ligands, with particular emphasis on the use of alkylidene complexes of the type Mo(NAr)(CHCMe(_2)R)(O-t-Bu)(_2) (R = Me, Ph) as initiators in living ring opening metathesis polymerization (ROMP).Chapter 1 highlights areas of transition metal chemistry of relevance to the general theme of this thesis, including recent advances in the ROMP of functionalized norbornene and norbornadiene monomers. Chapter 2 shows how a "Wittig like" capping reaction may be used to introduce a wide range of potentially useful functional groups onto the end of polymer chains generated via living ROMP. Amongst the functional groups introduced in this manner are CI, Me, OMe, CHO, CN, NMe(_2), NO(_2), NH(_2), CF(_3) and CO(_2)Me. Unusual 2-oxametallacycle intermediates have been observed in solution for benzaldehyde derivatives possessing electron withdrawing substituents. Chapter 3 develops the use of styrene and several of its derivatives as chain transfer agents in living ROMP. The use of substituted styrenes allows for functionalizadon of the start of the polymer chain. Chapter 4 investigates the "heteroatom exchange" reactivity of a variety of four coordinate molybdenum complexes. The exchange of multiply bonded oxo, imido and alkqrlidene units between such species, and to and from external substrates, has been investigated, and such studies have helped to identify bimolecular decomposition pathways responsible for the high molecular weight impurity sometimes observed in polymer samples prepared by living ROMP. Chapter 5 describes the synthesis and characterization of several niobium and tantalum half-sandwich imido complexes of the type Cp*M(NR)Cl(_2) (M = Nb, R = Me, 2,6-iPr(_2)C(_6)H(_3); M = Ta, R = 2,6-iPr(_2)C(_6)H(_3)). The "heteroatom exchange" reactivity of the imido unit in this environment has been investigated. The related half-sandwich alkylidene complex CpTa(CHCMe(_2)Ph)Cl(_2) has also been prepared and the exchange reactivity of the alkylidene ligand studied. Chapter 6 gives experimental details for chapters 2-5.
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Leclerc, Matthew. "Advances in the Fluorine Chemistry of Transition Metals and N-Heterocyclic Carbenes: Understanding Perfluoroalkyl and Fluoroalkene Reactivity." Thesis, Université d'Ottawa / University of Ottawa, 2017. http://hdl.handle.net/10393/36218.

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The importance of fluorine in a wide array of different areas within chemistry and biochemistry has been demonstrated time and time again. Fluorine-containing products range from essential substituents in pharmaceuticals and relatively long-lived tracers for PET imagining, to fluoropolymers with outstanding properties, to essential components in most of the strongest acids available to chemists today. Fluorine’s extreme electronegativity makes it a truly unique element, but its acute toxicity in its elemental F2 form makes it difficult to handle, prompting researchers to explore different options for incorporating this important element into a variety of different molecular scaffolds. Due to the remarkable thermodynamic and kinetic stabilities of C-F bonds, methods for forming and breaking these cleanly, and under relatively mild conditions, are in high demand. Fortunately, transition metals have greatly aided in this process. However, fluoroorganometallic chemistry is much less developed than transition metal chemistry involving hydrocarbons, and certainly less understood. One of the primary reasons for this relative dearth of fluoroorganometallic complexes is the difficulty associated with their synthesis. In this work, important steps towards perfluoroalkyl chain-growth within the coordination sphere of a transition metal will be presented, stemming in part from the synthesis and characterization of novel cobalt fluoride and bis(perfluoroalkyl) complexes. As important electrophiles, fluoroalkenes have primarily been used as monomers for the formation of important fluoropolymers. However, their direct reactivity with organics remains rare and is usually difficult to control, with limited substrate scopes. Herein, the formation of stable N-heterocyclic fluoroalkene adducts as versatile synthons for the incorporation of fluoroalkene fragments into various chemical environments will be introduced. By forming these adducts, the inconvenience of manipulating fluorinated gases in further reactions can be avoided, and the N-heterocyclic fragment is shown to aid in directing substitutions involving polyfluoroalkenyl imidazolium salts and organic nucleophiles to form a variety of C-E (E = C, N, O, S) and C-M bonds (M = Mn, Mo). The ease with which C-F bonds are manipulated in these systems is quite remarkable, as the substitution reactions occur cleanly and efficiently at room temperature, to form a variety of new bonds without the need for a transition metal. By expanding on the fundamental reactivity between N-heterocyclic carbenes and fluoroalkenes, attempts were made to correlate the observed reactivity with certain electronic and steric parameters unique to the utilized carbenes. Although a correlation has not yet been established, the effects of atypical steric constraints in a cyclic (alkyl)(amino)carbene were demonstrated, wherein the initial point of attack by the carbene on the fluoroalkene was modified. It is hoped that this work will eventually lead to new roles for organocatalysts in fluoroalkene transformations.
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Books on the topic "Transition metals – Reactivity"

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Claire, Kanwaljit S. Synthesis, structure and reactivity of diene(tricarbonyl) complexes of group 8 transition-metals. typescript, 1994.

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Elena, Soriano, José Marco-Contelles, and B. Alcaide. Computational mechanisms of Au and Pt catalyzed reactions. Springer, 2011.

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Cossy, Janine. Grignard Reagents: Reactivity with Transition Metals. De Gruyter, Inc., 2015.

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Nishibayashi, Yoshiaki. Transition Metal-Dinitrogen Complexes: Preparation and Reactivity. Wiley & Sons, Incorporated, John, 2019.

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Nishibayashi, Yoshiaki. Transition Metal-Dinitrogen Complexes: Preparation and Reactivity. Wiley & Sons, Limited, John, 2019.

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Nishibayashi, Yoshiaki. Transition Metal-Dinitrogen Complexes: Preparation and Reactivity. Wiley & Sons, Incorporated, John, 2019.

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C, Bruneau, and Dixneuf P. H, eds. Metal vinylidenes and allenylidenes in catalysis: From reactivity to applications in synthesis. Wiley-VCH, 2008.

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Bruneau, Christian, and Pierre Dixneuf. Metal Vinylidenes and Allenylidenes in Catalysis: From Reactivity to Applications in Synthesis. Wiley & Sons, Limited, John, 2008.

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Bruneau, Christian, and Pierre Dixneuf. Metal Vinylidenes and Allenylidenes in Catalysis: From Reactivity to Applications in Synthesis. Wiley & Sons, Incorporated, John, 2008.

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Metal-ligand interactions: Structure and reactivity. Kluwer Academic Publishers, 1996.

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Book chapters on the topic "Transition metals – Reactivity"

1

Armentrout, P. B. "Kinetic Energy Dependence of Ion-Molecule Reactions: From Triatomics to Transition Metals." In Structure/Reactivity and Thermochemistry of Ions. Springer Netherlands, 1987. http://dx.doi.org/10.1007/978-94-009-3787-1_6.

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Hofmann, P. "Applied MO Theory: Organometallic Structure and Reactivity Problems." In Quantum Chemistry: The Challenge of Transition Metals and Coordination Chemistry. Springer Netherlands, 1986. http://dx.doi.org/10.1007/978-94-009-4656-9_19.

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Dedieu, A., and S. Nakamura. "CO Activation and Reactivity in Organometallic Chemistry: Theoretical Studies." In Quantum Chemistry: The Challenge of Transition Metals and Coordination Chemistry. Springer Netherlands, 1986. http://dx.doi.org/10.1007/978-94-009-4656-9_20.

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Ghana, Priyabrata. "Open-Shell Heavier Tetrylidyne Complexes of Group 6 Transition Metals". У Synthesis, Characterization and Reactivity of Ylidyne and μ-Ylido Complexes Supported by Scorpionato Ligands. Springer International Publishing, 2018. http://dx.doi.org/10.1007/978-3-030-02625-7_3.

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Blomberg, M., U. Brandemark, I. Panas, P. Siegbahn, and U. Wahlgren. "Accurate Studies on the Structure and Reactivity of Transition Metal Complexes and Clusters." In Quantum Chemistry: The Challenge of Transition Metals and Coordination Chemistry. Springer Netherlands, 1986. http://dx.doi.org/10.1007/978-94-009-4656-9_1.

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Sugimoto, Hiroshi, Hui-Chan Tung, and Donald T. Sawyer. "The Formation, Characterization, and Reactivity of the Oxene Adduct of Tetra-Kis(2,6-Dichlorophenyl)Porphinato-Iron(III) Perchlorate in Acetonitrile." In Oxygen Complexes and Oxygen Activation by Transition Metals. Springer US, 1988. http://dx.doi.org/10.1007/978-1-4613-0955-0_33.

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Tkáč, A., and E. Hanušovská-Tkáčová. "Alternating Reactivity of Radicals Coordinated to Chelated Transition Metals or Metalloenzymes and Chemical Carcinogenesis." In Organic Free Radicals. Springer Berlin Heidelberg, 1988. http://dx.doi.org/10.1007/978-3-642-73963-7_105.

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Brec, R., and J. Rouxel. "Reactivity and Phase Transitions in Transition Metal Dichalcogenides Intercalation Chemistry." In Intercalation in Layered Materials. Springer US, 1986. http://dx.doi.org/10.1007/978-1-4757-5556-5_3.

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Ley, Steven V., and Caroline M. R. Low. "Transition Metal Carbonyls and Ultrasound." In Reactivity and Structure Concepts in Organic Chemistry. Springer Berlin Heidelberg, 1989. http://dx.doi.org/10.1007/978-3-642-74672-7_14.

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Angelici, R. J. "Binding and Reactivity of Thiophene-Type Ligands in Transition Metal Complexes and Clusters." In Transition Metal Sulphides. Springer Netherlands, 1998. http://dx.doi.org/10.1007/978-94-017-3577-3_4.

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Conference papers on the topic "Transition metals – Reactivity"

1

Andersson, Mats T., H. Gronbeck, L. Holmgren, and Arne Rosen. "Reactivity of small transition-metal clusters with CO." In SPIE's 1995 International Symposium on Optical Science, Engineering, and Instrumentation, edited by John W. Hepburn. SPIE, 1995. http://dx.doi.org/10.1117/12.220843.

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Eiden, G., S. Hanton, J. Harrington, D. Ritter, L. Sanders, and J. C. Weisshaar. "Gas phase transition metal species: electronic structure and reactivity." In ADVANCES IN LASER SCIENCE−IV. AIP, 1989. http://dx.doi.org/10.1063/1.38602.

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Ibrahim, Mohamad, Benoît Tremblay, Esmaïl Alikhani, and pascale soulard. "FTIR STUDY OF THE REACTIVITY OF HETERONUCLEAR SMALL TRANSITION METAL CLUSTER WITH CARBON MONOXIDE." In 73rd International Symposium on Molecular Spectroscopy. University of Illinois at Urbana-Champaign, 2018. http://dx.doi.org/10.15278/isms.2018.fb02.

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KUBAS, GREGORY J. "H2 BINDING AND REACTIVITY ON TRANSITION METAL COMPLEXES UNDERLYING BIOMIMETIC H2 PRODUCTION AND NEW MATERIALS FOR H2 STORAGE." In Proceedings of the International Symposium. WORLD SCIENTIFIC, 2009. http://dx.doi.org/10.1142/9789812838025_0007.

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Zhuang, Shiqiang, Xuan Shi, and Eon Soo Lee. "A Review on Non-PGM Cathode Catalysts for Polymer Electrolyte Membrane (PEM) Fuel Cell." In ASME 2015 13th International Conference on Fuel Cell Science, Engineering and Technology collocated with the ASME 2015 Power Conference, the ASME 2015 9th International Conference on Energy Sustainability, and the ASME 2015 Nuclear Forum. American Society of Mechanical Engineers, 2015. http://dx.doi.org/10.1115/fuelcell2015-49602.

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Abstract:
In recent years, people attach high attention to the energy problem owing to the energy shortage of the world. Since the price of energy resources significantly increases, it is a necessary requirement to develop new alternative sources of energy to replace non-renewable energy resources. Polymer electrolyte membrane (PEM) fuel cell technology is one of the promising fields of clean and sustainable power, which is based on direct conversion of fuel into electricity. However, at the present moment PEM fuel cell is unable to be successful commercialization. The main factor is the high cost of materials in catalyst layer which is a core part of PEM fuel cell. In order to reduce the overall system cost, developing active, inexpensive non-platinum group metal (non-PGM) electrode catalysts to replace currently used Platinum (Pt)-based catalysts is a necessary and essential requirement. This paper reviews several important kinds of non-PGM electro-catalysts with different elements, such as nitrogen, transition metal, and metal organic frameworks (MOF). Among these catalysts, transition metal nitrogen-containing complexes supported on carbon materials (M-N/C) are considered the most potential oxidation reduction reaction (ORR) catalysts. The main synthetic methods are high temperature heat treating (800–1000°C). The mechanical and electrochemical properties of the final product will be analyzed by several characterization methods. For example, a RRDE test will be used to measure electron transfer number and ORR reactivity, which are the most important electrochemical properties of the new catalyst. And the morphology, particle size, crystal phase and specific surface area can be analyzed with SEM, TEM, XRD and BET methods. Although great improvement has been achieved in non-PGM catalyst area of research, there are still some challenges in both ORR activity and stability of non-PGM catalysts. Consequently, how to improve the ORR activity and stability are the major challenge of non-PGM catalyst research and development. Based on the results achieved in this area, our future research direction is also presented and discussed in this paper.
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Reports on the topic "Transition metals – Reactivity"

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Armentrout, Peter. THERMOCHEMISTRY AND REACTIVITY OF TRANSITION METAL CLUSTERS AND THEIR OXIDES. Office of Scientific and Technical Information (OSTI), 2014. http://dx.doi.org/10.2172/1135682.

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Altman, Eric I. Structure-Reactivity Relationships in Multi-Component Transition Metal Oxide Catalysts FINAL Report. Office of Scientific and Technical Information (OSTI), 2015. http://dx.doi.org/10.2172/1222647.

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Reinig, Regina Rose. Synthesis and reactivity of paramagnetic late transition metal complexes supported by tris(oxazolinyl)phenylborate. Office of Scientific and Technical Information (OSTI), 2018. http://dx.doi.org/10.2172/1505192.

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