Dihydrogen bonding and activation of borohydride ligand via coordination to transition metals

Natalia Belkova

Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences

Natalia Belkova graduated from M.V.Lomonosov Moscow State University and received the PhD degree at INEOS. Her PhD work was awarded by Academia Europeae award for young scientists from Russia in 1997. After two years post-doctoral fellowship in St. Jude Children’s Research Hospital (Memphis, TN) she returned to INEOS where she received a D.Sc. degree and is leading researcher now. In 2016 she was elected a Professor of Russian Academy of Sciences. Her research interests are in hydrogen bonding in organometallic chemistry and their implication in mechanisms of reactions involving migration of hydrogen ions (proton transfer, hydride transfer) and structure/properties relationships.

Abstract

Transition metal coordination compounds containing the borohydride ligand, BH4 or LBH3 (L = amine), are an important class of compounds possessing many valuable properties and useful applications. Thus, they have been used as... [ view full abstract ]

Transition metal coordination compounds containing the borohydride ligand, BH₄ or LBH₃ (L = amine), are an important class of compounds possessing many valuable properties and useful applications. Thus, they have been used as selective reducing agents, precursors for the production of borides, hydrides and other inorganic materials, as well as in hydrogen production.

In this contribution the recent results on the reactivity of a variety of transition metal complexes (M = Cu, Ru, Ir) with BH₄ or LBH₃ ligands towards XH acids of different strength will be presented. It was studied by variable-temperature IR, UV-vis and NMR spectroscopies in low polar solvents in combination with DFT calculations [1-3]. Availability of several types of hydride ligands (MH, BHterm, BH^br) leads to a variety of mono-, bi- and trifurcate dihydrogen bonded complexes (Scheme 1), only few of which are the proton transfer reaction intermediates. The influence of coordination to the metal on the BH proton accepting ability and on the mechanism of the reactions involving proton transfer as a key step will be discussed. Crucial role of additional Lewis acidic centers in the reactivity of these complexes will be shown. Possible mechanisms of their transformation leading to H₂ evolution will be discussed including the mechanism of amine-boranes dehydrogenation.

References

[1]N. V. Belkova, E. V. Bakhmutova-Albert,E. I. Gutsul, V. I. Bakhmutov,I. E. Golub, O. A. Filippov, L. M. Epstein, M. Peruzzini, A. Rossin,F. Zanobini, E.S. Shubina Inorg. Chem., 2014, 53 (2), 1080.

[2] I. E. Golub, E. S. Gulyaeva, O. A. Filippov, V. P. Dyadchenko, N. V. Belkova, L. M. Epstein, D. E. Arkhipov, E. S. Shubina, The Journal of Physical Chemistry A 2015, 119, 3853

[3] I. E. Golub, O. A. Filippov, N. V. Belkova, L. M. Epstein, A. Rossin, M. Peruzzini, E. S. Shubina, Dalton Trans., 2016, 45, 9127

Acknowledgment: This work was supported by Russian Foundation for Basic Research (projects 16-03-00324, 15-53-78027)

Authors

Elena Shubina (Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences)
Natalia Belkova (Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences)
Oleg Filippov (Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences)
Lina Epstein (Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences)

Topic Area

B - Reactions of coordination compounds

Session

OS1-217a » Reactions of coordination compounds (14:30 - Monday, 3rd July, 217a)

Presentation Files

The presenter has not uploaded any presentation files.

Email Support • Blog • Privacy Policy • Cancellation Policy