PMID- 37947458
OWN - NLM
STAT- PubMed-not-MEDLINE
LR  - 20231122
IS  - 1463-9084 (Electronic)
IS  - 1463-9076 (Linking)
VI  - 25
IP  - 45
DP  - 2023 Nov 22
TI  - Photoelectron spectroscopic study of 2-naphthylnitrene and its thermal 
      rearrangement to cyanoindenes.
PG  - 31146-31152
LID - 10.1039/d3cp04064j [doi]
AB  - 2-Cyanoindene has recently been identified in the interstellar medium, however 
      current models cannot fully account for its formation pathways. Herein, we 
      identify and characterize 2-naphthylnitrene, which is prone to rearrange to 2- 
      and 3-cyanoindene, in the gas phase using photoion mass-selective threshold 
      photoelectron spectroscopy (ms-TPES). The adiabatic ionization energies (AIE) of 
      triplet nitrene ((3)A'') to the radical cation in its lowest-energy doublet 
      X̃(+)((2)A') and quartet a(+)((4)A') electronic states were determined to be 7.72 
      +/- 0.02 and 8.64 +/- 0.02 eV, respectively, leading to a doublet-quartet energy 
      splitting (DeltaE(D-Q)) of 0.92 eV (88.8 kJ mol(-1)). A ring-contraction mechanism 
      yields 3-cyanoindene, which is selectively formed under mild pyrolysis conditions 
      (800 K), while the lowest-energy isomer, 2-cyanoindene, is also observed under 
      harsh pyrolysis conditions at 1100 K. The isomer-selective assignment was 
      rationalized by Franck-Condon spectral modeling and by measuring the AIEs at 8.64 
      +/- 0.02 and 8.70 +/- 0.02 eV for 2- and 3-cyanoindene, respectively, in good 
      agreement with quantum chemical calculations.
FAU - Saraswat, Mayank
AU  - Saraswat M
AUID- ORCID: 0000-0003-1614-0262
AD  - Lehrstuhl fur Organische Chemie II, Ruhr-Universitat Bochum, Bochum 44780, 
      Germany. wolfram.sander@rub.de.
FAU - Portela-Gonzalez, Adrian
AU  - Portela-Gonzalez A
AUID- ORCID: 0000-0001-9859-4043
AD  - Lehrstuhl fur Organische Chemie II, Ruhr-Universitat Bochum, Bochum 44780, 
      Germany. wolfram.sander@rub.de.
FAU - Mendez-Vega, Enrique
AU  - Mendez-Vega E
AUID- ORCID: 0000-0001-5833-8520
AD  - Lehrstuhl fur Organische Chemie II, Ruhr-Universitat Bochum, Bochum 44780, 
      Germany. wolfram.sander@rub.de.
FAU - Karir, Ginny
AU  - Karir G
AUID- ORCID: 0000-0001-8896-9454
AD  - Lehrstuhl fur Organische Chemie II, Ruhr-Universitat Bochum, Bochum 44780, 
      Germany. wolfram.sander@rub.de.
FAU - Sander, Wolfram
AU  - Sander W
AUID- ORCID: 0000-0002-1640-7505
AD  - Lehrstuhl fur Organische Chemie II, Ruhr-Universitat Bochum, Bochum 44780, 
      Germany. wolfram.sander@rub.de.
FAU - Hemberger, Patrick
AU  - Hemberger P
AUID- ORCID: 0000-0002-1251-4549
AD  - Laboratory for Synchrotron Radiation and Femtochemistry, Paul Scherrer Institut 
      (PSI), Villigen CH-5232, Switzerland. patrick.hemberger@psi.ch.
LA  - eng
PT  - Journal Article
DEP - 20231122
PL  - England
TA  - Phys Chem Chem Phys
JT  - Physical chemistry chemical physics : PCCP
JID - 100888160
SB  - IM
EDAT- 2023/11/10 12:48
MHDA- 2023/11/10 12:49
CRDT- 2023/11/10 09:23
PHST- 2023/11/10 12:49 [medline]
PHST- 2023/11/10 12:48 [pubmed]
PHST- 2023/11/10 09:23 [entrez]
AID - 10.1039/d3cp04064j [doi]
PST - epublish
SO  - Phys Chem Chem Phys. 2023 Nov 22;25(45):31146-31152. doi: 10.1039/d3cp04064j.