Atom transfer reactions by

Table 2 Representative kinetic data for the nitrogen atom transfer reactions by osmium(VI) nitrido...

The Russian group [14, 17, 19, 20, 23—26, 29], have also measured many rate coefficients of H atom transfer reactions by the H —O2 explosion limits technique but several of the proposed mechanisms have yet to be confirmed. 

JM Berg, RH Hohn. Synthetic approaches to the mononuclear active sites of molyb-doenzymes catalytic oxygen atom transfer reactions by oxomolybdenum (IV, VI) complexes with saturation kinetics and without molybdenum (V) dimer formation. J Am Chem Soc 106 3035-3036, 1984. 

Knuehl BP T, Kajiwara A, Fischer H, Matyjaszewski, K. Characterization of Cu(II) bipyridine complexes in halogen atom transfer reactions by electron spin resonance. Macromolecules 2003 36 8291-8296. 

DETERMINATION OF THE BOTTLENECK REGIONS OF POTENTIAL ENERGY SURFACES FOR ATOM TRANSFER REACTIONS BY VARIATIONAL TRANSITION STATE THEORY... 

Sako, S., Shimada, K., Hirota, K., and Maki, Y, Photochemical oxygen atom transfer reaction by heterocyclic N-oxides involving a single electron transfer process. Oxidative demethylation of N,N-dimethylaniline, /. Am. Chem. Soc., 108, 6039,1986. 

N—Fe(IV)Por complexes. Oxo iron(IV) porphyrin cation radical complexes, [O—Fe(IV)Por ], are important intermediates in oxygen atom transfer reactions. Compound I of the enzymes catalase and peroxidase have this formulation, as does the active intermediate in the catalytic cycle of cytochrome P Q. Similar intermediates are invoked in the extensively investigated hydroxylations and epoxidations of hydrocarbon substrates cataly2ed by iron porphyrins in the presence of such oxidizing agents as iodosylbenzene, NaOCl, peroxides, and air. 

A number of chemiluminescent reactions have been studied by producing key reactants through pulsed electric discharge, by microwave dissociation, or by observing the reactions of atoms and free radicals produced in the inner cone of a laminar flame as they diffuse into the flame s cool outer cone (182,183). These are either combination reactions or atom-transfer reactions involving transfer of chlorine (184) or oxygen atoms (181,185—187), the latter giving excited oxides. 

Electronic excitation from atom-transfer reactions appears to be relatively uncommon, with most such reactions producing chemiluminescence from vibrationaHy excited ground states (188—191). Examples include reactions of oxygen atoms with carbon disulfide (190), acetylene (191), or methylene (190), all of which produce emission from vibrationaHy excited carbon monoxide. When such reactions are carried out at very low pressure (13 mPa (lO " torr)), energy transfer is diminished, as with molecular beam experiments, so that the distribution of vibrational and rotational energies in the products can be discerned (189). Laser emission at 5 p.m has been obtained from the reaction of methylene and oxygen initiated by flash photolysis of a mixture of SO2, 2 2 6 (1 )-... 

Pulsed source techniques have been used to study thermal energy ion-molecule reactions. For most of the proton and H atom transfer reactions studied k thermal) /k 10.5 volts /cm.) is approximately unity in apparent agreement with predictions from the simple ion-induced dipole model. However, the rate constants calculated on this basis are considerably higher than the experimental rate constants indicating reaction channels other than the atom transfer process. Thus, in some cases at least, the relationship of k thermal) to k 10.5 volts/cm.) may be determined by the variation of the relative importance of the atom transfer process with ion energy rather than by the interaction potential between the ion and the neutral. For most of the condensation ion-molecule reactions studied k thermal) is considerably greater than k 10.5 volts/cm.). 

The molybdenum and tunsten diphenylacetylene compounds have been chemically useful primarily as precursors to the quadruple metal-metal bonded dimers [M(Por)]2, formed by solid-state vacuum pyrolysis reactions. However. Mo(TTP)()/"-PhC CPh) is also a useful substrate in atom-transfer reactions, reacting with Sx or Cp2TiS i to form Mo(TTP)=S. The reaction can be reversed by treatment of Mo(TTP)=S with PPh (which removes sulfur as PhxP=S) and PhC CPh. The order of preference for ligand binding to molybdenum 11) has been established to be PPh < PhC CPh < 4-picoline. ... 

Quantification of antioxidant action usually relies on the reducing ability of antioxidants, measured either by electron transfer, reaction [16.15], or by hydrogen atom transfer reactions, reaction [16.16] ... 

Radical reactions used in synthesis include additions to double bonds, ring closure, and atom transfer reactions. Several sequences of tandem reactions have been developed that can close a series of rings, followed by introduction of a substituent. Allylic stannanes are prominent in reactions of this type. 

In Sections III(l) and 111(2) the lability principle has been illustrated for processes involving the transfer of weakly bound electrons, including the reactions of solvated and trapped electrons and F-centers and processes of electrochemical generation of solvated electrons. In Sections IV and V, it will be illustrated also by atom transfer reactions and, in particular, by reactions involving adsorbed atoms. 

The distance xx describes the distance along the x-coordinate over which G increases by RT. We assume that motion along the x-coordinate is diffusive. This will be true for encounters, rearrangement of the ionic atmosphere or the rotation of solvent molecules. We further assume that at some distance xj the atom-transfer reaction becomes possible with a rate constant k. The diffusive kinetic equation then becomes (18), where the step function S(xt) = 0... 

A new generation of oxorhenium compounds has now been prepared. They catalyze oxidation reactions of a different type, and appear to function by a different mechanism. They are oxorhenium(V) compounds that form usually metastable dioxorhenium(VII) intermediates. The mechanisms feature Rev(0)-to-ReVII(0)2 interconversions and catalyze oxygen atom transfer reactions. The mechanisms show a certain diversity as to the steps that enter in a kinetic sense. Yet the schemes presented in this review show a great deal of similarity in their overall mode of action. 

Bromides are less reactive than the corresponding iodides in atom transfer processes. However, activated bromides such as diethyl bromomalonate [36] and bromomalonitrile [53] react with olefins under Et3B/02 initiation. Kha-rasch type reactions of bromotrichloromethane with alkenes are also initiated by Et3B/02 [41]. On the other hand, a remarkable Lewis acid effect was reported by Porter. Atom-transfer reactions of an a-bromooxazolidinone amide with alkenes are strongly favored in the presence of Lewis acids such as Sc(0Tf)3 or Yb(0Tf)3, this reaction was successively applied to the... 

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