Abstract
The mechanism of the newly reported route for surface-assisted covalent coupling of terminal alkynes on Ag(111) is unraveled by density functional theory based transition state calculations. We illustrate that the reaction path is fundamentally different from the classical coupling schemes in wet chemistry. It is initiated by the covalent coupling between two molecules instead of single-molecule dehydrogenation. The silver substrate is found to play an important role stabilizing the intermediate species by chemical bonds, although it is hardly active electronically in the actual coupling step. The dimer intermediate is concluded to undergo two subsequent dehydrogenation processes expected to be rate-limiting according to the comparatively large barriers, which origin is discussed.
Original language | English |
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Pages (from-to) | 3181-3187 |
Number of pages | 7 |
Journal | Journal of Physical Chemistry C |
Volume | 118 |
Issue number | 6 |
DOIs | |
State | Published - 13 Feb 2014 |