PMID- 32208698
OWN - NLM
STAT- PubMed-not-MEDLINE
LR  - 20200514
IS  - 1520-5215 (Electronic)
IS  - 1089-5639 (Linking)
VI  - 124
IP  - 19
DP  - 2020 May 14
TI  - Isomer-Selective Threshold Photoelectron Spectra of Phenylnitrene and Its Thermal 
      Rearrangement Products.
PG  - 3836-3843
LID - 10.1021/acs.jpca.0c01134 [doi]
AB  - The photoionization of phenylnitrene was investigated by photoion mass-selected 
      threshold photoelectron spectroscopy in the gas phase. Flash vacuum pyrolysis of 
      phenyl azide at 480  degrees C produces the nitrene, which subsequently rearranges at 
      higher temperatures affording three isomeric cyanocyclopentadienes, in contrast 
      to low-temperature trapping experiments. Temperature control of the reactor and 
      threshold photoelectron spectra allows for optimizing the generation of 
      phenylnitrene or its thermal rearrangement products, as well as obtaining 
      vibrational information for the corresponding ions. The adiabatic ionization 
      energies (AIE) of the triplet nitrene ((3)A(2)) to the radical cation in its 
      lowest-energy doublet ((2)B(2)) and quartet ((4)A(1)) spin states were determined 
      to 8.29 +/- 0.01 and 9.73 +/- 0.01 eV, respectively. Vibrational frequencies of ring 
      breathing modes were measured at 500 +/- 80 and 484 +/- 80 cm(-1) for both the 
      [Formula: see text]((2)B(2)) and [Formula: see text]((4)A(1)) cationic states, 
      respectively. The AIE differ from the values previously reported; hence, we 
      revise the doublet-quartet energy splitting of the phenylnitrene radical cation 
      to 1.44 eV, in excellent agreement with composite methods and coupled cluster 
      calculations, but considerably higher than the literature reference (1.1 eV).
FAU - Mendez-Vega, Enrique
AU  - Mendez-Vega E
AUID- ORCID: 0000-0001-5833-8520
AD  - Lehrstuhl fur Organische Chemie II, Ruhr-Universitat Bochum, 44780 Bochum, 
      Germany.
FAU - Sander, Wolfram
AU  - Sander W
AUID- ORCID: 0000-0002-1640-7505
AD  - Lehrstuhl fur Organische Chemie II, Ruhr-Universitat Bochum, 44780 Bochum, 
      Germany.
FAU - Hemberger, Patrick
AU  - Hemberger P
AUID- ORCID: 0000-0002-1251-4549
AD  - Laboratory for Synchrotron Radiation and Femtochemistry, Paul Scherrer Institut, 
      CH-5232 Villigen, Switzerland.
LA  - eng
PT  - Journal Article
DEP - 20200403
PL  - United States
TA  - J Phys Chem A
JT  - The journal of physical chemistry. A
JID - 9890903
SB  - IM
EDAT- 2020/03/27 06:00
MHDA- 2020/03/27 06:01
CRDT- 2020/03/27 06:00
PHST- 2020/03/27 06:00 [pubmed]
PHST- 2020/03/27 06:01 [medline]
PHST- 2020/03/27 06:00 [entrez]
AID - 10.1021/acs.jpca.0c01134 [doi]
PST - ppublish
SO  - J Phys Chem A. 2020 May 14;124(19):3836-3843. doi: 10.1021/acs.jpca.0c01134. Epub 
      2020 Apr 3.