Covalent C–N Bond Formation through a Surface Catalyzed Thermal 
Cyclodehydrogenation

Piskun, I.; Blackwell, R.; Jornet-Somoza, J.; Zhao, F.; Rubio, A.; Louie, S. G.; Fischer, F. R.

doi:10.1021/jacs.9b13507

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Covalent C–N Bond Formation through a Surface Catalyzed Thermal Cyclodehydrogenation

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Jornet-Somoza, J.
Nano-Bio Spectroscopy Group and ETSF, Universidad del País Vasco UPV/EHU;
Theory Group, Theory Department, Max Planck Institute for the Structure and Dynamics of Matter, Max Planck Society;

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Rubio, A.
Nano-Bio Spectroscopy Group and ETSF, Universidad del País Vasco UPV/EHU;
Theory Group, Theory Department, Max Planck Institute for the Structure and Dynamics of Matter, Max Planck Society;
Center for Computational Quantum Physics (CCQ), The Flatiron Institute;

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ja9b13507_si_001.pdf
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Citation

Piskun, I., Blackwell, R., Jornet-Somoza, J., Zhao, F., Rubio, A., Louie, S. G., et al. (2020). Covalent C–N Bond Formation through a Surface Catalyzed Thermal Cyclodehydrogenation. Journal of the American Chemical Society, 142(8), 3696-3700. doi:10.1021/jacs.9b13507.

Cite as: https://hdl.handle.net/21.11116/0000-0005-E64E-1

Abstract

The integration of substitutional dopants at predetermined positions along the hexagonal lattice of graphene-derived polycyclic aromatic hydrocarbons is a critical tool in the design of functional electronic materials. Here, we report the unusually mild thermally induced oxidative cyclodehydrogenation of dianthryl pyrazino[2,3-g]quinoxalines to form the four covalent C–N bonds in tetraazateranthene on Au(111) and Ag(111) surfaces. Bond-resolved scanning probe microscopy, differential conductance spectroscopy, along with first-principles calculations unambiguously confirm the structural assignment. Detailed mechanistic analysis based on ab initio density functional theory calculations reveals a stepwise mechanism featuring a rate determining barrier of only ΔE^⧧ = 0.6 eV, consistent with the experimentally observed reaction conditions.