Rafael Navrátil

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Helium-tagging predissociation spectroscopy in the visible spectral range (He@VisPD) is shown for Rhodamine 123, Rhodamine 110, and Rhodamine 110's silver salt (silver carboxylate). It is shown that the spectra reflect single-photon absorption. The helium-tagged ions are in the ground vibrational state, and the He@VisPD spectra feature the Franck-Condon(More)
The nominal temperature range of cryogenic radio-frequency ion traps has recently been extended down to T=2.3 K. Whereas in situ He tagging of mass-selected ions embedded in dense helium buffer gas is becoming common for recording IR spectra through photofragmentation of small and large ions, much less activity is devoted to the field of cold chemistry,(More)
Diazirinylidene (c-CN2) is formally the simplest of the N-heterocyclic carbenes. The intermediacy of this elusive species in the fragmentation of butyl 3-bromodiazirine-3-carboxylate (1a) with pent-4-en-1-ols and their sodium alkoxides in DMF is supported by the formation of 2-oxabicyclo[4.1.0]heptanes and dipentenoxymethanes. These products result from an(More)
We demonstrate the application of infrared photodissocation spectroscopy for determination of the Fe═O stretching frequencies of high-valent iron(IV)-oxo complexes [(L)Fe(O)(X)]2+/+ (L = TMC, N4Py, PyTACN, and X = CH3CN, CF3SO3, ClO4, CF3COO, NO3, N3). We show that the values determined by resonance Raman spectroscopy in acetonitrile solutions are on(More)
3-Halo-3-phenyl-3H-diazirines (halogen = Br or Cl) undergo a dissociative single-electron transfer from alkyllithiums (RLi) in THF-based solvent mixtures. The resulting 3-phenyldiazirinyl radical, observed by EPR spectroscopy, is eventually transformed to benzonitrile. In Et2O, 2 equiv of RLi add to both nitrogens of halodiazirine N═N bond, affording(More)
In biology, high valent oxo-iron(IV) species have been shown to be pivotal intermediates for functionalization of C-H bonds in the catalytic cycles of a range of O2-activating iron enzymes. This work details an electronic-structure investigation of [FeIV(O)(LNHC)(NCMe)]2+ (LNHC =(More)
The generation of iron(V) nitride complexes, which are targets of biomimetic chemistry, is reported. Temperature-dependent ion spectroscopy shows that this reaction is governed by the spin-state population of their iron(III) azide precursors and can be tuned by temperature. The complex [(MePy2 TACN)Fe(N3 )]2+ (MePy2(More)
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