Computational study of the C - H bond activation in ethylene on a binuclear ruthenium complex

Samat Tussupbayev, Sergei F. Vyboishchikov

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Abstract

The reaction is substantially exothermic - the calculated total reaction enthalpy ΔHo298 between 1 + 6C2H 4 and 26 + 3C2H6 is about -90 kcal·mol-1. The reaction occurs through a number of stages, each including ethylene coordination, at least two hydride migrations, and ethane elimination. The rate-determining step of the mechanism is the initial coordination of the first ethylene molecule to the reactant 1 to give the ethylene π complex (H)2CpRu(μ-H)2RuCp(η 2-C2H4) (2). The free energy barrier is about 27 kcal·mol-1 according to the static DFT calculations. Metadynamic simulations of the coordination process yield a ΔG 298 barrier of about 20 kcal ·mol-1. Another high-barrier step is the ethylene coordination to CpRu(η2: η1-CH=CH2)2RuCp (25) to give the final product 26. In total, the tide reaction is a sophisticated multistep reaction with a large number of possible pathways. The mechanism of the reaction is largely determined by the flexibility of hydride ligands and by cooperation between both Ru centers.

Original languageEnglish (US)
Pages (from-to)3681-3692
Number of pages12
JournalOrganometallics
Volume27
Issue number15
DOIs
StatePublished - Aug 11 2008

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