title: Thermochemical studies of pyrazolide.
abstract: The 351.1 nm photoelectron spectrum of 1-pyrazolide anion has been measured. The 1-pyrazolide ion is produced by hydroxide (HO(-)) deprotonation of pyrazole in a flowing afterglow ion source. The electron affinity (EA) of the 1-pyrazolyl radical has been determined to be 2.938 +/- 0.005 eV. The angular dependence of the photoelectrons indicates near-degeneracy of low-lying states of 1-pyrazolyl. The vibronic feature of the spectrum suggests significant nonadiabatic effects in these electronic states. The gas phase acidity of pyrazole has been determined using a flowing afterglow-selected ion flow tube; Delta(acid)G(298) = 346.4 +/- 0.3 kcal mol(-1) and Delta(acid)H(298) = 353.6 +/- 0.4 kcal mol(-1). The N-H bond dissociation energy (BDE) of pyrazole is derived to be D(0)(pyrazole, N-H) = 106.4 +/- 0.4 kcal mol(-1) from the EA and the acidity using a thermochemical cycle. In addition to 1-pyrazolide, the photoelectron spectrum demonstrates that HO(-) deprotonates pyrazole at the C5 position to generate a minor amount of 5-pyrazolide anion. The photoelectron spectrum of 5-pyrazolide has been successfully reproduced by a Franck-Condon (FC) simulation based on the optimized geometries and the normal modes obtained from B3LYP/6-311++G(d,p) electronic structure calculations. The EA of the 5-pyrazolyl radical is 2.104 +/- 0.005 eV. The spectrum exhibits an extensive vibrational progression for an in-plane CCN bending mode, which indicates a substantial difference in the CCN angle between the electronic ground states of 5-pyrazolide and 5-pyrazolyl. Fundamental vibrational frequencies of 890 +/- 15, 1110 +/- 35, and 1345 +/- 30 cm(-1) have been assigned for the in-plane CCN bending mode and two in-plane bond-stretching modes, respectively, of X (2)A' 5-pyrazolyl. The physical properties of the pyrazole system are compared to the isoelectronic systems, pyrrole and imidazole.
authors.affiliation: JILA, University of Colorado and National Institute of Standards and Technology, Department of Chemistry and Biochemistry, University of Colorado, Boulder, Colorado 80309-0440, USA.
authors.forename: Adam J
authors.initials: AJ
authors.lastname: Gianola
authors.forename: Takatoshi
authors.initials: T
authors.lastname: Ichino
authors.forename: Shuji
authors.initials: S
authors.lastname: Kato
authors.forename: Veronica M
authors.initials: VM
authors.lastname: Bierbaum
authors.forename: W Carl
authors.initials: WC
authors.lastname: Lineberger