title: The phenylnitrene rearrangement in the inner phase of a hemicarcerand.
abstract: The photochemistry of phenyl azide 1 and 13C-labeled phenyl azide 13C-1 incarcerated inside a hemicarcerand 4 was investigated. Low-temperature photolysis of hemicarceplex 41 and 413C-1 yields incarcerated 1-azacyclohepta-1,2,4,6-tetraene 42 and 413C-2 (18-50%), respectively, which were characterized by low-temperature FT-IR and 1H NMR and 13C NMR spectroscopy. After correction for the hemicarcerand-induced upfield shift, the 13C chemical shifts of incarcerated 13C-2 compare very well (Deltadelta </= 3.5 ppm) with the GIAO chemical shift tensors calculated at the PBE1PBE/6-311G++(2d,2p) level. Incarcerated 2 has a lifetime of 32 min at 194.4 K and decomposes by ring contraction to singlet phenylnitrene 1PN. 1PN intersystem crosses to triplet phenylnitrene, which reacts with the surrounding host. From the time dependence of the characteristic ketenimine IR absorption of 2 at 1886 cm-1, the rate constant, kobs, for decay of 2 was measured between 198.3 and 174.3 K. Under the assumption that the intersystem-crossing rate constant kISC and the ring-expansion rate constant k1 in pentane (Gritsan, N. P.; Zhu, Z.; Hadad, C. M.; Platz, M. S. J. Am. Chem. Soc. 1999, 121, 1202) and in the inner phase are identical, the rate constant k' = 1011.0 +/- 0.7 x exp(-12.3 +/- 0.6 kcal/mol/RT) for the ring contraction of 2 was calculated. The activation energy compares very well with those calculated at the CASPT2N/6-311G(2d,p) (Karney, W. L.; Borden, W. T. J. Am. Chem. Soc. 1997, 119, 1378) and B3LYP/6-311+G(2d,p) (Tsao, M.-L.; Platz, M. S. J. Am. Chem. Soc. 2003, 125, 12014) level of theory.
authors.affiliation: Department of Chemistry and Chemical Biology, Rutgers-The State University of New Jersey, 610 Taylor Road, Piscataway, New Jersey 08854, USA. warmuth@rutchem.rutgers.edu
authors.forename: Ralf
authors.initials: R
authors.lastname: Warmuth
authors.forename: Slawomir
authors.initials: S
authors.lastname: Makowiec