Thermal activation of tert-butyl nitrite on Pt(111): tert-butoxy dehydrogenation and oxametallacycle formation Academic Article uri icon

abstract

  • The adsorption and thermal reactions of an alkyl nitrite, t-C4H9ONO, on Pt(111) are reported. Dissociative chemisorption at the weak (171 kJ/mol)RO-NO bond accompanies adsorption at 115 K, forming adsorbed t-C4H9O and NO. During heating to 200 K, some t-C4H9O dehydrogenates at the -carbon (methyl group) to form a proposed oxametallacycle species that dehydrogenates further upon heating to 250 K. tert-Butyl alcohol, t-C4H9OH, desorbs in three coverage-dependent peaks (200, 250, and 300 K) attributable to hydrogenation of both t-C4H9O and the oxametallacycle. The yields and reaction paths depend on the initial dose of t-C4H9ONO. Vibrational modes of the oxametallacycle were compared for several plausible structures, with modes calculated using density functional theory. Among these structures, a four-membered oxametallacycle ring (containing only one Pt atom in the ring) gave the best agreement with the experimental data. Finally, a reaction path potential energy diagram was constructed.

published proceedings

  • LANGMUIR

author list (cited authors)

  • Ihm, H., Medlin, J. W., Barteau, M. A., & White, J. M.

citation count

  • 15

complete list of authors

  • Ihm, H||Medlin, JW||Barteau, MA||White, JM

publication date

  • February 2001