Many important catalyzed bond-transformations involve donor-acceptor interactions at the reaction center - the transition metal and, only relatively recently, the heavier main-group elements making parts of the so-called frustrated Lewis pairs (FLPs).[1] [2], [3] The conformation of an FLP complex has a large effect on its reactivity towards H2. In a series of R'2P-BR2 compounds with the dative p-bond, the reactivity depends on the geometry of the P and B centers because of the properties of the p-type overlap between the adjustment lone pair of P and empty p-orbital of B. A dynamics-driven balance between acidity and basicity of the fragments of FLPs is essential for understanding the thermodynamics (reaction energy change) and the kinetics (barrier) of hydrogen activation. One prominent example is the reduction of imines by zwitterionic complex (R2')2PH-C6F4-BH(R2)2. The recently proposed mechanism has been refined just recently using the direct dynamics calculations. Complementary to the hydrogen transfer to carbon-nitrogen unsaturated bonds, we address the dynamics of carbonyl-borane FLPs. Recently, our suggestion of the possibility of catalytic reduction of carbonyl compounds with B(C6F5)3 and H2 in a manner similar to the reduction of C=N bonds (imines) in the presence of only B(C6F5)3 and H2, has been confirmed by experiment � our most recent results and perspective are to be presented.  [1]           Power, P. P., Nature, 2010 , 463, 171.[2]           Stephan D. W.; Erker G.; Angew. Chem. Int. Ed., 2010 , 49, 46.[3]           a) Nyhlen, J.; Privalov, T., J. Mol. Catal. A: Chem. 2010 , 324, 97; b) Nyhl�n, J; Privalov, T., Dalton Transactions, 2009 , 5780; c) Nyhl�n, J; Privalov, T., Eur. J. Inorg. Chem, 2009 , 275; d) Privalov, T., Eur. J. Inorg. Chem, 2009 , 2229; e) Privalov, T. I., Chem. Eur. J., 2009 , 15, 1825; f) Privalov, T., Dalton Transactions, 2009 , 1321.

Heavier main-group elements and transition metals: Theory and computation of active complexes

245th National Meeting (2013)

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