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Metal carbonyl anions ([M(CO)nL]- ) are more halogenophilic than most common nucleophiles, including [RS]- and carbanions; Halogenophilic attack is the main alternative to the addition-elimination (AdNE) substitution mechanism in the reactions of [M(CO)nL]- with vinyl and aryl halides; The direction of [M(CO)nL]- attack in vinyl halide is strongly dependant on its structure and can be predicted by the developed computational model; The reactivity of vinyl halides in AdNE substitution correlates with their p* LUMO energies, while no correlation with s*(C-Hal) orbital energies is found for their reactivity in halogenophilic reactions; The reactivity of vinyl halides in halogenophilic reactions can be described by a linear combination of DFT energies of Hal+ abstraction from VinHal and Hal+ affinity of [M(CO)nL]-;