Deuterium and Hydrogen Tunneling in the Hydrogenation of 4-Oxocyclohexa-2,5-dienylidene

作者：Henkel Stefan; Ertelt Melanie; Sander Wolfram^*

来源：Chemistry - A European Journal, 2014, 20(25): 7585-7588.

DOI：10.1002/chem.201402064

• carbenes
• EPR spectroscopy
• hydrogen activation
• IR spectroscopy
• matrix isolation

4-Oxocyclohexa-2,5-dienylidene is a highly reactive triplet ground state carbene that is hydrogenated in solid H-2, HD, and D-2 at temperatures as low as 3 K. The mechanism of the insertion of the carbene into dihydrogen was investigated by IR and EPR spectroscopy and by kinetic studies. H or D atoms were observed as products of the reaction with H-2 and D-2, respectively, whereas HD produces exclusively D atoms. The hydrogenation shows a very large kinetic isotope effect and remarkable isotope selectivity, as was expected for a tunneling reaction. The experiments, therefore, provide clear evidence for both hydrogen tunneling and the rare deuterium tunneling in an intermolecular reaction.

• 出版日期2014-6-16