Abstract
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)3H, 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: σMH → σ*OH interaction leads to the proton transfer to hydride ligand, nM → σ*OH leads to the metal atom protonation, nN → σ*MH implies the metal hydride deprotonation, and σMH → 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 Brønsted and Lewis acids. The ease of polarization of M-H bonds in complexes CpM(CO)3H determines their reactivity as proton and hydride ion donors.
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Dedicated to the 60th anniversary of foundation of the A. N. Nesmeyanov Institute of Organoelement Compounds of the Russian Academy of Sciences.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2428—2433, November, 2014.
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Filippov, O.A., Golub, I.E., Osipova, E.S. et al. Activation of M—H bond upon the complexation of transition metal hydrides with acids and bases. Russ Chem Bull 63, 2428–2433 (2014). https://doi.org/10.1007/s11172-014-0758-5
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DOI: https://doi.org/10.1007/s11172-014-0758-5