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Volumn 131, Issue 33, 2009, Pages 11698-11700

Isolable photoreactive polysilyl radicals

Author keywords

[No Author keywords available]

Indexed keywords

2-PROPANOL; DFT CALCULATION; DICHLOROSILANES; DISPROPORTIONATIONS; ELECTRON-ACCEPTING; IRRADIATION EXPERIMENTS; ONE-STEP METHODS; PHOTOSTABLE; SILYL RADICAL; TRIETHYLSILANE;

EID: 69049085599     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja905097b     Document Type: Article
Times cited : (21)

References (37)
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    • (d) Power, P. Chem. Rev. 2003, 103, 789.
    • (2003) Chem. Rev , vol.103 , pp. 789
    • Power, P.1
  • 12
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    • Kira, M.; Badugu, R. In Handbook of Photochemistry and Photobiology; Nalwa, H. S., Ed.; American Scientific Publishers: Stevenson Ranch, CA, 2003; 1.
    • (d) Kira, M.; Badugu, R. In Handbook of Photochemistry and Photobiology; Nalwa, H. S., Ed.; American Scientific Publishers: Stevenson Ranch, CA, 2003; Vol. 1.
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    • Photochemistry of stable organic radicals was reported. Canepa, M.; Fox, M. A.; Whitesell, J. K. J. Org. Chem. 2001, 66, 3886.
    • Photochemistry of stable organic radicals was reported. Canepa, M.; Fox, M. A.; Whitesell, J. K. J. Org. Chem. 2001, 66, 3886.
  • 18
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    • Synthesis of 1: a hexane solution (4 mL) of t-Bu2MeSiLi (B, 0.5 g, 3.0 mmol) was added to a frozen hexane solution (10 mL) of (t-Bu2MeSi)2HSiSiHCl2 (A, 0.44 g, 1.0 mmol, The frozen mixture was warmed up to 0°C and stirred for 1 h in the dark. All volatile compounds were then evaporated in vacuum, and 5 mL of dry hexane were added. Keeping the solution at -30°C for 12 h yielded 0.45 g (65, of orange prisms (Figure 1a, insert) identified as 1 by X-ray crystallography (Figure S1, EPR spectroscopy (Figure 1a, trapping reactions (Scheme 1, paths a, b, and non-preparative synthesis from other precursors (Scheme 1, paths c, d, UV-vis (Figure 3a, 230 nm (9300, 268 nm (13130, 278 nm (12200, 350 nm (3360, 428 nm 800
    • 2 (A) (0.44 g, 1.0 mmol). The frozen mixture was warmed up to 0°C and stirred for 1 h in the dark. All volatile compounds were then evaporated in vacuum, and 5 mL of dry hexane were added. Keeping the solution at -30°C for 12 h yielded 0.45 g (65%) of orange prisms (Figure 1a, insert) identified as 1 by X-ray crystallography (Figure S1), EPR spectroscopy (Figure 1a), trapping reactions (Scheme 1, paths a, b), and non-preparative synthesis from other precursors (Scheme 1, paths c, d); UV-vis (Figure 3a): 230 nm (9300), 268 nm (13130), 278 nm (12200), 350 nm (3360), 428 nm (800).
  • 19
    • 69049087494 scopus 로고    scopus 로고
    • 4 The EPR spectra of 2 at high resolution and in toluene glass (not reported previously) are given in Figures S5 and S6, respectively.
    • 4 The EPR spectra of 2 at high resolution and in toluene glass (not reported previously) are given in Figures S5 and S6, respectively.
  • 20
    • 69049095826 scopus 로고    scopus 로고
    • 2HSi). The synthesis and spectroscopy of these radicals will be reported elsewhere.
    • 2HSi). The synthesis and spectroscopy of these radicals will be reported elsewhere.
  • 21
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    • See Supporting Information for the CIF file and experimental details Figure S2
    • See Supporting Information for the CIF file and experimental details (Figure S2).
  • 22
    • 69049110709 scopus 로고    scopus 로고
    • α) = 113 G.
    • α) = 113 G.
  • 23
    • 69049111525 scopus 로고    scopus 로고
    • 3SiLi, i.e., using eq 1; see the Supporting Information.
    • 3SiLi, i.e., using eq 1; see the Supporting Information.
  • 28
    • 69049102851 scopus 로고    scopus 로고
    • Calculations were carried out at the UB3LYP/TZVP//UB3LYP/6-31G(d) level using the Gaussian 03, Revision D.02 series of programs: Frisch, M. J.; et al. Gaussian 03, revision D.02; Gaussian, Inc.: Wallingford, CT, 2004 (see the Supporting Information for the full list of authors and for the calculations' details).
    • Calculations were carried out at the UB3LYP/TZVP//UB3LYP/6-31G(d) level using the Gaussian 03, Revision D.02 series of programs: Frisch, M. J.; et al. Gaussian 03, revision D.02; Gaussian, Inc.: Wallingford, CT, 2004 (see the Supporting Information for the full list of authors and for the calculations' details).
  • 30
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    • Disilene 4 was reported previously: Sekiguchi, A.; Inoue, S.; Ichinohe, M.; Arai, Y. J. Am. Chem. Soc. 2004, 126, 9626.
    • Disilene 4 was reported previously: Sekiguchi, A.; Inoue, S.; Ichinohe, M.; Arai, Y. J. Am. Chem. Soc. 2004, 126, 9626.
  • 32
    • 0003670973 scopus 로고    scopus 로고
    • Rappoport, Z, Apeloig, Y, Eds, John Wiley & Sons: Chichester, U.K
    • (b) Gaspar, P. P.; West, R. In The Chemistry of Organic Silicon Compounds; Rappoport, Z., Apeloig, Y., Eds.; John Wiley & Sons: Chichester, U.K., 1998; Vol. 2.
    • (1998) The Chemistry of Organic Silicon Compounds , vol.2
    • Gaspar, P.P.1    West, R.2
  • 33
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    • The experiment was carried out in the EPR tube upon irradiation with a 1 kW mercury lamp inside the cavity of an EPR spectrometer. Full conversion of 1 under these conditions occurs in 200 s. We note that the recorded second-order decay of 1 upon irradiation is not proof for the bimolecular reaction since the quantum yield of the reaction was not measured. The kinetic curves are given in Figure S8
    • The experiment was carried out in the EPR tube upon irradiation with a 1 kW mercury lamp inside the cavity of an EPR spectrometer. Full conversion of 1 under these conditions occurs in 200 s. We note that the recorded second-order decay of 1 upon irradiation is not proof for the bimolecular reaction since the quantum yield of the reaction was not measured. The kinetic curves are given in Figure S8.
  • 34
    • 69049089577 scopus 로고    scopus 로고
    • In radical 2 only the SOMO-1 → SOMO transition occurs upon irradiation with λ > 400 nm. In radical 1 both SOMO-1 → SOMO and SOMO → LUMO transitions occur, and therefore photoexcited 1 may exhibit enhanced electron-donating properties (Figure S9).
    • In radical 2 only the SOMO-1 → SOMO transition occurs upon irradiation with λ > 400 nm. In radical 1 both SOMO-1 → SOMO and SOMO → LUMO transitions occur, and therefore photoexcited 1 may exhibit enhanced electron-donating properties (Figure S9).
  • 36
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    • Related (not photoinduced) mechanism of hydrogen abstraction by organic radicals was reported: (a) Litwinienko, G.; Ingold, K. U. Acc. Chem. Res. 2007, 40, 222.
    • Related (not photoinduced) mechanism of hydrogen abstraction by organic radicals was reported: (a) Litwinienko, G.; Ingold, K. U. Acc. Chem. Res. 2007, 40, 222.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.