Relevant bibliographies by topics / Outer-sphere complex

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  2. Dissertations / Theses
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Academic literature on the topic 'Outer-sphere complex'

Author: Grafiati
Published: 4 June 2021
Last updated: 15 February 2022

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Journal articles on the topic "Outer-sphere complex"

1

Fanali, S., L. Ossicini, and M. Sinibaldi. "Capillary isotachophoretic study of outer-sphere complex formation." Chromatographia 23, no. 11 (1987): 811–13. http://dx.doi.org/10.1007/bf02311404.

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Veenboer, Richard M. P., Alba Collado, Stéphanie Dupuy, et al. "Inner-Sphere versus Outer-Sphere Coordination of BF4– in a NHC-Gold(I) Complex." Organometallics 36, no. 15 (2017): 2861–69. http://dx.doi.org/10.1021/acs.organomet.7b00345.

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Chandrawat, Uttra, Aditya Prakash, and Raj N. Mehrotra. "Kinetics and mechanism of the oxidation of the sulphite ion by the Mn(III)–cydta complex ion." Canadian Journal of Chemistry 73, no. 9 (1995): 1531–37. http://dx.doi.org/10.1139/v95-190.

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The reinvestigated oxidation of S(IV), HSO3−/SO32−ions, by [Mn(cydta)(OH)]− confirmed that S(IV) is oxidized in two parallel paths; the order with respect to [S(IV)] is one in one of the paths and two in the other. The nature of the dependence of the rate on [H+] is also confirmed. However, the rapid scan of the reaction mixture and measurement of the initial absorbance of the reaction mixture at different wavelengths at the beginning of the reaction suggest an outer-sphere mechanism. The rate parameters are of the same order as obtained in known reactions of an outer-sphere mechanism and this mechanism is further supported by the Marcus cross relation. Keywords: kinetics, outer-sphere mechanism, [Mn(cydta)]−, SO32−.
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Pankhurst, James R., Nicola L. Bell, Markus Zegke, et al. "Inner-sphere vs. outer-sphere reduction of uranyl supported by a redox-active, donor-expanded dipyrrin." Chemical Science 8, no. 1 (2017): 108–16. http://dx.doi.org/10.1039/c6sc02912d.

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Van Leeuwen, Herman P., and Raewyn M. Town. "Protonation effects on dynamic flux properties of aqueous metal complexes." Collection of Czechoslovak Chemical Communications 74, no. 10 (2009): 1543–57. http://dx.doi.org/10.1135/cccc2009091.

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The degree of (de)protonation of aqueous metal species has significant consequences for the kinetics of complex formation/dissociation. All protonated forms of both the ligand and the hydrated central metal ion contribute to the rate of complex formation to an extent weighted by the pertaining outer-sphere stabilities. Likewise, the lifetime of the uncomplexed metal is determined by all the various protonated ligand species. Therefore, the interfacial reaction layer thickness, μ, and the ensuing kinetic flux, Jkin, are more involved than in the conventional case. All inner-sphere complexes contribute to the overall rate of dissociation, as weighted by their respective rate constants for dissociation, kd. The presence of inner-sphere deprotonated H2O, or of outer-sphere protonated ligand, generally has a great impact on kd of the inner-sphere complex. Consequently, the overall flux can be dominated by a species that is a minor component of the bulk speciation. The concepts are shown to provide a good description of experimental stripping chronopotentiometric data for several protonated metal–ligand systems.
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Weiss, Robert, та Andreas M. H. Grimmeiss. "Outer-sphere-CT-Wechselwirkungen zwischen einem organischen π-Radikaldikation und Hauptgruppenelement-Hexahalogenat-Komplexen / Outer-Sphere-CT-Interactions between an Organic π-Radical Dication and Main-Group Hexahalogenate Complexes". Zeitschrift für Naturforschung B 44, № 11 (1989): 1447–50. http://dx.doi.org/10.1515/znb-1989-1120.

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1:1-Electrolytes of the type [tris(dimethylamino)cyclopropendiylium]2+ElX62- have been synthesized for the first time (El = Sn, Te; X = Cl, Br). Analysis of their UV spectra points to a novel OSCT-interaction within these ion pairs in which the complex anion acts as the donor. With 48-electron systems as SnX62- the bromo complex is the better donor than the chloro complex whereas with 50-electron systems TeX62- the reverse behaviour is observed. These contrasting tendencies can be explained by a simple MO model, according to which SnX62- anions interact with the organic acceptor via a HOMO of tlu- symmetry, whereas anions of the type TeX62- employ their alg*-HOMO.
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Lim, Jia Hui, Xenia Engelmann, Sacha Corby, Rakesh Ganguly, Kallol Ray, and Han Sen Soo. "C–H activation and nucleophilic substitution in a photochemically generated high valent iron complex." Chemical Science 9, no. 16 (2018): 3992–4002. http://dx.doi.org/10.1039/c7sc05378a.

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Bonnet, Célia S., Pascal H. Fries, Serge Crouzy, and Pascale Delangle. "Outer-Sphere Investigation of MRI Relaxation Contrast Agents. Example of a Cyclodecapeptide Gadolinium Complex with Second-Sphere Water." Journal of Physical Chemistry B 114, no. 26 (2010): 8770–81. http://dx.doi.org/10.1021/jp101443v.

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Akashi, Haruo, Mami Nishiura, Masayasu Mori, and Takashi Shibahara. "Effect of outer sphere anions on the structure and color of nitrosylpentaamminechromium complex." Inorganica Chimica Acta 331, no. 1 (2002): 290–95. http://dx.doi.org/10.1016/s0020-1693(02)00687-4.

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de Aguirre, Adiran, Ignacio Funes-Ardoiz, and Feliu Maseras. "Computational Characterization of Single-Electron Transfer Steps in Water Oxidation." Inorganics 7, no. 3 (2019): 32. http://dx.doi.org/10.3390/inorganics7030032.

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The presence of single-electron transfer (SET) steps in water oxidation processes catalyzed by first-row transition metal complexes has been recently recognized, but the computational characterization of this type of process is not trivial. We report a systematic theoretical study based on density functional theory (DFT) calculations on the reactivity of a specific copper complex active in water oxidation that reacts through two consecutive single-electron transfers. Both inner-sphere (through transition state location) and outer-sphere (through Marcus theory) mechanisms are analyzed. The first electron transfer is found to operate through outer-sphere, and the second one through inner-sphere. The current work proposes a scheme for the systematic study of single-electron transfer in water oxidation catalysis and beyond.
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Dissertations / Theses on the topic "Outer-sphere complex"

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Hwang, Yu Sik. "Adsorption Of Naturally-Occurring Dicarboxylic Acids At The Hematite/Water Interface." The Ohio State University, 2008. http://rave.ohiolink.edu/etdc/view?acc_num=osu1226256959.

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Kotze, Izak Aldert. "Self-association of [PtII(1,10-Phenanthroline)(N-pyrrolidyl-N-(2,2-dimethyl-propanoyl)thiourea)]+ and non-covalent outer-sphere complex formation with fluoranthene through cation-π interactions : a high resolution 1H and DOSY NMR study". Thesis, Stellenbosch : University of Stellenbosch, 2009. http://hdl.handle.net/10019.1/1796.

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Naklicki, Mark L. (Mark Leonard) Carleton University Dissertation Chemistry. "Inner-sphere and outer-sphere perturbations of the ruthenium-cyanamide bond in mononuclear and dinuclear pentaammineruthenium complexes of 1,4-dicyanamidobenzene ligands." Ottawa, 1995.

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Pullen, Sonja. "Mimicking the Outer Coordination Sphere in [FeFe]-Hydrogenase Active Site Models : From Extended Ligand Design to Metal-Organic Frameworks." Doctoral thesis, Uppsala universitet, Molekylär biomimetik, 2017. http://urn.kb.se/resolve?urn=urn:nbn:se:uu:diva-318975.

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Biomimetic catalysis is an important research field, as a better understanding of nature´s powerful toolbox for the conversion of molecules can lead to technological progress. [FeFe]-hydrogenases are very efficient catalysts for hydrogen production. These enzymes play a crucial role in the metabolism of green algae and certain cyanobacteria. Their active site consists of a diiron complex that is embedded in an interactive protein matrix. In this thesis, two pathways for mimicking the outer coordination sphere effects resulting from the protein matrix are explored. The first is the construction of model complexes containing phosphine ligands that are coordinated to the iron center as well as covalently linked to the bridging ligand of the complex. The effect of such linkers is an increased energy barrier for the rotation of the Fe(CO2)(PL3)-subunit, which potentially could stabilize a terminal hydride that is an important intermediate in the proton reduction cycle. The second pathway follows the incorporation of [FeFe]-hydrogenase active site model complexes into metal-organic frameworks (MOFs). Resulting MOF-catalysts exhibit increased photocatalytic activity compared to homogenous references due to a stabilizing effect on catalytic intermediates by the surrounding framework. Catalyst accessibility within the MOF and the influence of the framework on chemical reactivity are examined in the work presented. Furthermore, an initial step towards application of MOF-catalysts in a device was made by interfacing them with electrodes. The work of this thesis highlights strategies for the improvement of biomimetic model catalysts and the knowledge gained can be transferred to other systems mimicking the function of enzymes.
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Wang, Xiaoguang Stanbury David McNeill. "Mechanism of the outer-sphere oxidation of aqueous L-Cysteine and of iodide in acetonitrile by a series of iron (III) complexes." Auburn, Ala., 2007. http://repo.lib.auburn.edu/Send%2011-10-07/WANG_XIAOGUANG_13.pdf.

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Hadzovic, Alen. "Outer sphere hydrogenation of ketones catalyzed by ruthenium(II) hydride complexes." 2007. http://link.library.utoronto.ca/eir/EIRdetail.cfm?Resources__ID=478889&T=F.

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Pan, Amanda, and 潘家穎. "The Kinetic Studies of the Outer-Sphere Electron Transfer Reaction between Protocatechuic Acid and Pentacyanoferrate(III) Complexes." Thesis, 2006. http://ndltd.ncl.edu.tw/handle/42768263851637946221.

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碩士<br>東海大學<br>化學系<br>95<br>The reductions of [Fe(CN)5L]2-(L=4-cyano-pyridine, isonicotinamide, 4,4’-bipyridine, pyridine, pyrazine)complexes by protocatechuic acid have been subjected to a detailed kinetic study in the range of pH 5 – 9. The rate law of the reaction is interpreted as a rate determining reaction between Fe(III) complexes and the protocatechuic acid in the form of H2cat-COO-(k1), Hcat-COO2-(k2), and cat-COO3-(k3), depending on the pH of the solution, follow by a rapid scavenge of the protocatechuic acid radicals by Fe(III) complex. With given Ka1, Ka2, and Ka3, the rate constants are k1 = 1.5×102(cp), 3.9×101(isn), 8.0×101(bpy), and 5.4×102 M-1s-1(pz)；k2 = 3.0×105(cp), 1.2×105(isn),1.1×105(bpy), 3.4×104(py), and 2.9×105 M-1s-1(pz)；k3 = 3.2×108(cp), 1.6×108(isn), 9.2×107(bpy), and 5.5×107(py), respectively, atμ= 0.10 M LiClO4, T = 25℃. The kinetic results are compatible with the Marcus theory for out-sphere electron transfer. Moreover, the detailed theoretical analysis indicates that, the tremendously large rate difference with k1:k2:k3～1:103:106, arises predominantly from the equilibrium barrier of the different acid forms of the protocatechuic acid, and is rather insensitive to the intrinsic reactivities and the charge effect of the reactants.
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WANG, PEI-LIAN, and 王佩蓮. "NMR relaxation analysis on the formation of outer-sphere-complexes between chloroform and tris (acetylacetonato) chromium (III) in solutions." Thesis, 1988. http://ndltd.ncl.edu.tw/handle/15625471373911055551.

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"A study of the outer sphere interaction of some octahedral coordinated cobalt (III) complexes by 59Co nuclear magnetic resonance methods." Chinese University of Hong Kong, 1992. http://library.cuhk.edu.hk/record=b5887735.

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by Chung Sai Cheong.<br>Thesis (M.Phil.)--Chinese University of Hong Kong, 1993.<br>Includes bibliographical references (leaves 94-99).<br>DESCRIPTIVE NOTE<br>ABSTRACT --- p.iii<br>ACKNOWLEDGEMENTS --- p.v<br>Chapter CHAPTER ONE: --- INTRODUCTION --- p.1<br>Chapter CHAPTER TWO: --- EXPERIMENTAL --- p.6<br>Chapter 2.1 --- Synthesis --- p.6<br>Chapter 2.2 --- NMR Measurement --- p.6<br>Chapter 2.2.1 --- Solid State 59Co NMR --- p.6<br>Chapter 2.2.2 --- Solution NMR --- p.7<br>Chapter 2.2.2.1 --- 59Co NMR Measurements --- p.7<br>Chapter 2.2.2.2 --- 13C NMR Measurements --- p.8<br>Chapter 2.3 --- UV-Vis Spectral Measurements --- p.9<br>Chapter 2.4 --- Computer Simulation --- p.10<br>Chapter CHAPTER THREE: --- QUANTITATIVE CORRELATION OF SHIELDING ANISOTROPY AND NQCC - APPLICATION TO SOLVATION STUDIES OF OCTAHEDRAL COBALT (III)COMPLEXES<br>Chapter 3.1 --- Introduction --- p.11<br>Chapter 3.2 --- Theory --- p.15<br>Chapter 3.3 --- Results and Discussion --- p.20<br>Chapter 3.3.1 --- The 59Co NMR Powder Spectrum of Diamagnetic Cobalt Complexes --- p.20<br>Chapter 3.3.2 --- The Correlation of NQCC with Chemical Shift Anisotropy in the Solid State --- p.34<br>Chapter 3.3.3 --- Application of Equation 3.16in Solution Studies --- p.39<br>Chapter 3.3.3.1 --- The Chemical Shift --- p.39<br>Chapter 3.3.3.2 --- The Effective Correlation Time --- p.48<br>Chapter 3.3.3.3 --- The Nuclear Quadrupole Coupling Constant --- p.49<br>Chapter 3.4 --- Summary --- p.51<br>Chapter CHAPTER FOUR: --- 59Co AND 13C RELAXATION OF Co(acac)3 IN HYDROGEN BONDING (KALOMETHANE) SOLVENTS<br>Chapter 4.1 --- Introduction --- p.53<br>Chapter 4.2 --- Results and Discussion --- p.57<br>Chapter 4.2.1 --- The Static NMR Powder Spectrum Co(acac)3 --- p.57<br>Chapter 4.2.2 --- Chemical shift --- p.60<br>Chapter 4.2.3 --- Relaxation --- p.67<br>Chapter 4.2.3.1 --- The 13C Relaxation --- p.67<br>Chapter 4.2.3.2 --- The 59Co Relaxation --- p.71<br>The Spin Rotation Interaction --- p.71<br>The Temperature Behaviour of Relaxa- tion Rate --- p.72<br>The Nuclear Quadru- pole Coupling Constant --- p.76<br>The Correlation Time --- p.82<br>Chapter 4.3 --- Summary --- p.90<br>Chapter CHAPTER FIVE: --- CONCLUSION --- p.91<br>REFERENCES --- p.94
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O, Wylie Wing Nien. "Late Transition Metal Complexes Bearing Functionalized N-Heterocyclic Carbenes and the Catalytic Hydrogenation of Polar Double Bonds." Thesis, 2012. http://hdl.handle.net/1807/36294.

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Late transition metal complexes of silver(I), rhodium(I), ruthenium(II), palladium(II) and platinum(II) containing a nitrile-functionalized N-heterocyclic carbene ligand (C-CN) were prepared. The nitrile group on the C–CN ligand was shown to undergo hydrolysis under basic conditions, leading to a silver(I) carbene complex with a primary-amido functional group, and a trimetallic complex of palladium(II) with a partially hydrolyzed C–N–N–C donor ligand. The reduction of a nitrile-functionalized imidazolium salt in the presence of nickel(II) chloride under mild conditions yielded an axially chiral square-planar nickel(II) complex containing a unique primary-amino functionalized N-heterocyclic carbene ligand (C-NH2). A transmetalation reaction moved this chelating C–NH2 ligand from nickel(II) to ruthenium(II), osmium(II), and iridium(III), yielding important catalysts for the hydrogenation of polar double bonds. The ruthenium(II) complex, [Ru(p-cymene)(C–NH2)Cl]PF6 catalyzed the transfer and H2-hydrogenation of ketones. The bifunctional hydride complex, [Ru(p-cymene)(C–NH2)H]PF6, which contains a Ru–H/N–H couple showed no activity under catalytic conditions unless when activated by a base. The outer-sphere mechanism involving bifunctional catalysis of ketone reduction is disfavored according to experimental and theoretical studies and an inner-sphere mechanism is proposed involving the decoordination of the amine donor from the C–NH2 ligand. The ruthenium(II) complex [RuCp*(C–NH2)py]PF6 showed higher activity than the iridium(III) complex [IrCp*(C–NH2)Cl]PF6 in the hydrogenation of ketones. This ruthenium(II) complex also catalyzes the hydrogenation of an aromatic ester, a ketimine, and the hydrogenolysis of styrene oxide. We proposed an alcohol-assisted outer sphere bifunctional mechanism for both systems based on experimental findings and theoretical calculations. The cationic iridium(III) hydride complex, [IrCp*(C–NH2)H]PF6 , was prepared and this failed to react with a ketone in the absence of base. The crucial role of the alkoxide base was demonstrated in the activation of this hydride complex in catalysis. Calculations support the proposal that the base deprotonates the amine group of this hydride complex and triggers the migration of the hydride to the η5-Cp* ring producing a neutral iridium(I) amido complex. This system contains an active Ir–H/N–H couple required for the outer sphere hydrogenation of ketones in the bifunctional mechanism.
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Books on the topic "Outer-sphere complex"

1

Gribble, Jacquelin D. Kinetics of outer-sphere electron transfer reactions in non-aqueous solutions. 1989.

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Anderson, Kim A. Kinetics of outer-sphere electron transfer reactions in non-aqueous solvents. 1989.

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Book chapters on the topic "Outer-sphere complex"

1

Lancaster, Kyle M. "Biological Outer-Sphere Coordination." In Molecular Electronic Structures of Transition Metal Complexes I. Springer Berlin Heidelberg, 2011. http://dx.doi.org/10.1007/430_2011_49.

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Vogler, Arnd, and Horst Kunkely. "Photochemistry of transition metal complexes induced by outer-sphere charge transfer excitation." In Topics in Current Chemistry. Springer Berlin Heidelberg, 1990. http://dx.doi.org/10.1007/3-540-52568-8_1.

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Schmickler, Wolfgang. "Theoretical considerations of electron-transfer reactions." In Interfacial Electrochemistry. Oxford University Press, 1996. http://dx.doi.org/10.1093/oso/9780195089325.003.0011.

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Chemical and electrochemical reactions in condensed phases are generally quite complex processes; only outer-sphere electron-transfer reactions are sufficiently simple that we have reached a fair understanding of them in terms of microscopic concepts. In this chapter we give a simple derivation of a semiclassical theory of outer-sphere electron-transfer reactions, which was first systematically developed by Marcus and Hush in a series of papers. A more advanced treatment will be presented in Chapter 19. We begin with qualitative considerations. During the course of an outer-sphere electron-transfer reaction, the reactants get very close, up to a few Ångstroms, to the electrode surface. Electrons can tunnel over such a short distance, and the reaction would be very fast if nothing happened but the transfer of an electron. In fact, outer-sphere reactions are fast, but they have a measurable rate, and an energy of activation of typically 0.2 - 0.4 eV, since electron transfer is accompanied by reorganization processes of atoms and molecules that require thermal activation. While the reacting complex often has the same or similar structure in the oxidized and reduced form, metal-ligand bonds are typically shorter in the complex with the higher charge, which is also more strongly solvated. So the reaction is accompanied by a reorganization of both the complex, or inner sphere, and the solvation sheath, or outer sphere (see Fig. 6.1). These processes require an energy of activation and slow the reaction down. A natural question is: In which temporal order do the reorganization processes and the proper electron transfer take place? The answer is given by the Frank-Condon principle, which in this context, states: First the heavy particles of the inner and outer sphere must assume a suitable intermediate configuration, then the electron is exchanged isoenergetically, and finally the system relaxes to its new equilibrium configuration. A simple illustration is given in Fig. 6.2, where we have drawn potential energy surfaces for the reduced and the oxidized state as a function of two generalized reaction coordinates representing the positions of particles in the inner and outer sphere.
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Largier, Niklaus. "The Media of Sensation." In Anthropology of Catholicism. University of California Press, 2017. http://dx.doi.org/10.1525/california/9780520288423.003.0025.

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This chapter discusses the significance of medieval practices of prayer both for the modern rediscovery of media and for the anthropology of sensation. It demonstrates how medieval theories of reading, prayer, and contemplation thematize ways in which specific media—words, images, and music—are to be used in order to produce sensual and affective cognition. In doing so, these theories develop a sophisticated understanding of media on one side, and a specific understanding of the human soul as a sphere of evocation of possible sensation and affect on the other side. In working through this complex intersection of media and soul-formation I focus on this very notion of possibility, its significance in the context of an ‘anthropology of Catholicism’, and its presence in catholic discourses from the Middle Ages up to the twentieth century. Through discussion of the source texts an understanding of the seemingly established anthropological distinction between “inner man” and “outer man,” “interiority” and “exteriority” is challenged and what remains is a radically different way of thinking about interiority.
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Sposito, Garrison. "Exchangeable Ions." In The Chemistry of Soils. Oxford University Press, 2016. http://dx.doi.org/10.1093/oso/9780190630881.003.0013.

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In Section 3.4, the cation exchange capacity, or CEC, of particulate soil humus is defined as the maximum number of moles of proton charge per kilogram that can be desorbed by a metal cation under prescribed conditions. Thus, CEC for particulate humus is equal to the maximum absolute value of the negative net proton charge. Operationally, this maximum value is measured typically as the surface excess of Ba2+ adsorbed by humus at pH 8.2 (Eq. 3.5). Extending this concept to soils, one can define the CEC as the maximum number of moles of readily exchangeablemetal cation charge per unit mass of dry soil that can be extracted under prescribed conditions. In this more general context, CEC refers to metal cations that adsorb on soil particles in either outer sphere surface complexes or the diffuse ion swarm (Fig. 7.2). In alkaline soils, the common readily exchangeable cations are Ca2+, Mg2+, Na+, and K+, whereas in acidic soils, this group expands to include Al3+, and its complexes AlOH2+, Al(OH)2+, and AlSO+4. Following the operational paradigm for soil humus, one concludes that the measurement of soil CEC involves not only the desorption of protons, but also the replacement of the population of readily exchangeable adsorbed metal cations at a selected pH value (usually pH 7–8) by a chosen cation. Laboratory procedures for measuring CEC are described in Methods of Soil Analysis, listed in For Further Reading at the end of this chapter. In alkaline soils, the replacing cation chosen is often Na+ or Ca2+, whereas in acidic soils and for soil humus, the replacing cation of choice is Ba2+. These cations, in turn, are typically displaced from soil particle surfaces by Mg2+ to measure the surface excess. A conceptual definition of CEC can be developed in terms of the surface charge balance concepts introduced in Chapter 7. Consider first a soil in which a net positive surface excess of anions does not occur, such as the Mollisol example discussed in Section 8.1. In this case, the only adsorbed ions are Ca2+ and Cl-. The CEC of this soil may be defined by a special case of the charge-balance condition in Eq. 7.3a: ∆qex (max) ≡ CEC
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Reports on the topic "Outer-sphere complex"

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Atwood, J. (Comparison of group transfer, inner sphere and outer sphere electron transfer mechanisms of organometallic complexes). Office of Scientific and Technical Information (OSTI), 1990. http://dx.doi.org/10.2172/6286368.

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Atwood, J. (Comparison of group transfer, inner sphere and outer sphere electron transfer mechanisms of organometallic complexes: Progress report). Office of Scientific and Technical Information (OSTI), 1990. http://dx.doi.org/10.2172/5573799.

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Atwood, J. [Comparison of group transfer, inner sphere and outer sphere electron transfer mechanisms of organometallic complexes: Progress report]. Office of Scientific and Technical Information (OSTI), 1990. http://dx.doi.org/10.2172/10140197.

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(Comparison of group transfer, inner shere and outer sphere electron transfer mechanisms for organometallic complexes). Office of Scientific and Technical Information (OSTI), 1991. http://dx.doi.org/10.2172/6106339.

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[Comparison of group transfer, inner shere and outer sphere electron transfer mechanisms for organometallic complexes]. Summary. Office of Scientific and Technical Information (OSTI), 1991. http://dx.doi.org/10.2172/10106564.

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