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Enzymatic and Model Carboxylation and Reduction Reactions for Carbon Dioxide Utilization (Paperback, Softcover reprint of the original 1st ed. 1990)
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Enzymatic and Model Carboxylation and Reduction Reactions for Carbon Dioxide Utilization (Paperback, Softcover reprint of the original 1st ed. 1990)
Series: NATO Science Series C, 314
Expected to ship within 10 - 15 working days
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The activation of carbon dioxide by transition metal complexes has
been extensively studied. both experimentally and theoretically. 1
Central reactions in this chemistry are the insertion of C02 into
M-X bonds. where X = H. C. 0. and N. (eq. 1-4). We are presently
investigating the mechanistic aspects of these reaction processes
and will herein deSCribe our current level of understanding.
Comparisons of the pathway of the carbon-carbon bond fonning
process in transition metal chemistry with the well known analogous
chemistry involving organolithium reagents will be presented.
Furthermore. the role of these reaction types in both homogeneous
and heterogenous catalytic processes leading to useful chemicals
will be elaborated. _OM> (1) lMt-H + ~ lMlopi _OM> (2) [Mt-R
+ C0. 2 [M]0. 2CR _OM> (3) [Mt-OR+ ~ [M]0. 2COR _OM> (4)
[Mt-NR2 + C0. 2 [M]~CNR2 Insertion of C02 into the Metal-Hydride
Bond. The reaction of anionic group 6 (Cr. Mo. W) transition metal
hydrides with carbon dioxide to afford metalloformates occurs
readlly at ambient temperature and 2 reduced pressures of carbon
dioxide. This insertion process is referred to the normal pathway
(Scheme 1). There are no documented cases of C02 insertion into the
metal hydride bond to provide the alternative. metallocarboxylic
acid. isomer (referred in Scheme 1 as abnormal). 3 Recent
theoretical studies ascribe this preference to an unfavorable
electrostatic interaction and poorer orbital overlap in the latter
pro 4 cess. Nevertheless.
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