Activation of M-H bond upon the complexation of transition metal hydrides with acids and basesстатья
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Дата последнего поиска статьи во внешних источниках: 11 марта 2017 г.
Аннотация:Features of the electronic structure of adducts of transition metal hydride complexes (Cp*M(dppe)H, dppe is the 1,2-(diphenylphosphino)ethane, M = Fe, Ru, Os; CpM(CO)(3)H, M = Mo, W) with acids and bases were analyzed with the ADF2014 program using energy decomposition analysis (EDA) by the Ziegler-Rauk method combined with the natural orbitals for chemical valence theory (ETS-NOCV). The nature of orbital interactions in the complex determines the reaction pathway: sigma(MH) -> sigma*(OH) interaction leads to the proton transfer to hydride ligand, n(M) -> sigma*(OH) leads to the metal atom protonation, n(N) -> sigma*(MH) implies the metal hydride deprotonation, and sigma(MH) -> n*(B) corresponds to the hydride transfer to Lewis acid. It was shown that M-H bond polarization change has the similar character upon the formation of complexes with Bronsted and Lewis acids. The ease of polarization of M-H bonds in complexes CpM(CO)(3)H determines their reactivity as proton and hydride ion donors.