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Decarbonylation of complex iridium carbonyls in solution: A problem in chemical dynamics
Author(s) -
D'Agostino Riccardo,
Gerardi Sergio,
Molinari Ettore
Publication year - 1975
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.550070208
Subject(s) - decarbonylation , chemistry , carbon monoxide , reaction rate constant , kinetics , iridium , chemical reaction , diffusion , isomerization , solvent , chemical kinetics , decomposition , photochemistry , thermodynamics , organic chemistry , catalysis , physics , quantum mechanics
The kinetics of decarbonylation of [Ir(CO)(dp) 2 ]Cl and [IrCl(CO) 2 (Ph 3 P) 2 ] has been studied in different solvents, at temperatures between −25° and +70°C, by means of reactors of defined fluid dynamics which allow a separation to be made between “physical” and “chemical” rate constants. Chemical rate constants have been found to depend markedly on the diffusion coefficients of carbon monoxide in the various solvents. The process of decarbonylation has been described, for both reactions, by the sequence: structural isomerization, characterized by a very low preexponential factor, decomposition of the less stable isomer against the solvent's barrier, and diffusion of carbon monoxide to the gas–liquid interface. The kinetic problems involved in the determination of rate constants and their implications have been emphasized.