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Transition metal bases, correlation between

In the development of effective catalytic oxidation systems, there is a qualitative correlation between the desirability of the net or terminal oxidant, (OX in equation 1 and DO in equation 2) and the complexity of its chemistry and the difficulty of its use. The desirability of an oxidant is inversely proportional to its cost and directly proportional to the selectivity, rate, and stability of the associated oxidation reaction. The weight % of active oxygen, ease of deployment, and environmental friendliness of the oxidant are also key issues. Pertinent data for representative oxidants are summarized in Table I (4). The most desirable oxidant, in principle, but the one with the most complex chemistry, is O2. The radical chain or autoxidation chemistry inherent in 02-based organic oxidations, whether it is mediated by redox active transition metal ions, nonmetal species, metal oxide surfaces, or other species, is fascinatingly complex and represents nearly a field unto itself (7,75). Although initiation, termination, hydroperoxide breakdown, concentration dependent inhibition... [Pg.69]

Modem methods based on density-functional theory (DFT) can describe relative activation barriers of organometallic reactions, i.e. relative reactivities, as well as the transition-metal NMR chemical shifts of the reactant complexes involved. It is thus possible to reproduce or rationalize observed correlations between these properties or to predict new ones. NMR/reactivity correlations that could be reproduced theoretically ("intrinsic correlations") are summarized. Newly predicted NMR/ reactivity correlations are discussed for the ethylene polymerization with V(=0-X)R3 or V(=Y)R3 catalysts. When X or Y are varied (X = A1H3, Li+, SbF5, H+ Y = NH, O, S, Se), both... [Pg.240]


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Correlation between

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Metallic correlation

Metals correlations

Transitional metal bases, correlation

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