Heterocyclic ligands on ruthenium-based catalysts have been observed to greatly enhance the reaction rate for production of aldehydes from alkynes.  The final stage of this process involves a two-step H-atom transfer that transforms a hydroxycarbene to aldehyde via the ligand heteroatom.  The reaction barriers are comparable to hydrogen stretching vibrational energies, and the lowest energy quantum states of the H atom sample a large domain on the potential surface that connects the relevant intermediates.  In an effort to probe the kinetic isotope shift and other quantum effects of this phase of the reaction, we solve the vibrational Schrodinger equation explicitly for the H atom dynamics along this complex potential energy surface.  The surface is mapped along three dimensions by density functional calculations using correlation consistent basis sets.  The vibrational energies and eigenfunctions for hydrogen and for deuterium are determined by numerical integration using the finite element method.

Hydrogen atom dynamics in the formation of acetaldehyde on a heterocyclic organotransition metal catalyst

248th National Meeting (2014)

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