Structure Analysis of Photo-induced Triplet Phenylnitrene Using Synchrotron Radiation

Chemistry Letters

Volumn 32, Issue 10, 2003, Pages 922-923

  Kawano, Masaki ^b   Takayama, Terufumi ^a   Uekusa, Hidehiro ^a   Ohashi, Yuji ^a   Ozawa, Yoshiki ^c   Matsubara, Koudatsu ^c   Imabayashi, Hidekazu ^c   Mitsumi, Minoru ^c   Toriumi, Koshiro ^c  

^a TOKYO INSTITUTE OF TECHNOLOGY   (Japan)

^b JAPAN SCIENCE AND TECHNOLOGY AGENCY   (Japan)

^c UNIVERSITY OF HYOGO   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

BENZENE DERIVATIVE; PHENYLNITRENE; UNCLASSIFIED DRUG;

ARTICLE; CHEMICAL BOND; CRYSTAL STRUCTURE; LIGHT; STRUCTURE ANALYSIS; SYNCHROTRON; ULTRAVIOLET IRRADIATION; X RAY ANALYSIS;

EID: 0348140876     PISSN: 03667022     EISSN: None     Source Type: Journal    
DOI: 10.1246/cl.2003.922     Document Type: Article

References (20)

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12. D. Hashizume and Y. Ohashi, J. Chem. Soc., Perkin Trans. 2, 1999, 1689.
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15. X-ray data were collected on an X-ray vacuum camera equipped with an IP area detector.
16. The crystalline-state photoreaction of 2 was monitored by IR spectroscopy in a KBr matrix. Photolysis of 2 at 7 K caused clear spectral changes with isosbestic points, indicating a unique product, nitrene.
17. 2 group. A few restraints were applied to two disordered ammonium cations where the thermal temperature factors were anisotropically refined with constraints forcing the same values for each corresponding atom. Crystallographic data reported in this paper have been deposited with Cambridge Crystallographic Data Centre as supplementary publication no. CCDC 215565-215568.
18. We observed such a short contact between a dinitrogen molecule and a triplet diphenylcarbene in a crystal. See the Ref. 2d.
19. The triplet state of the product was confirmed by ESR as expected from Ref. 1c. Ab initio molecular orbital calculations were carried out using the GAUSSIAN 98 program. Optimized geometries were obtained at the (U)B3LYP/6-31G* and CASSCF/6-31G* levels of theory. For a triplet nitrene the active space used in CASSCF calculations comprised of 6 electrons in 6 MOs (two π and three π* MOs plus a σ one) denoted as CASSCF(6,6).
20. Because the result of the CASSCF calculation depends on the combination of the selected active spaces, several combinations and sizes of them were tested. Despite many attempts, the CASSCF calculations using the active spaces larger than (6,6) have been yet unsuccessful, resulting in non-convergence of SCF calculations. See the following excellent review about calculations on open-shell molecules: T. Bally and W. T. Borden, Rev. Comput. Chem., 13, 1 (1999).