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Volumn 128, Issue 39, 2006, Pages 12685-12692

The Si-Si effect on ionization of β-disilanyl sulfides and selenides

Author keywords

[No Author keywords available]

Indexed keywords

ELECTRON DEFICIENCY; GEOMETRY DEPENDENT INTERACTIONS; IONIZATION ENERGIES;

EID: 33749526868     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja0573514     Document Type: Article
Times cited : (14)

References (87)
  • 29
    • 33749509508 scopus 로고    scopus 로고
    • note
    • The reason for the greater effectiveness of a C-Sn σ-MO than C-Si σ-MO is a better energy match of orbital energies and consequent greater interaction. That is, the HOMO ionization energy for sulfur 3p lone pair orbitals in thioethers is much lower than that of oxygen and nitrogen lone pair orbitals in ethers and amines. Consequently, while a C-Si σ-MO is a good energy match for an oxygen or nitrogen lone pair orbital, the lower energy C-Sn σ-MO is a better energy match for a sulfur or selenium lone pair HOMO than a C-Si σ-MO.
  • 31
    • 33749510184 scopus 로고    scopus 로고
    • note
    • 18 for 2,2- bis(trimethylsilyl)-1,3-dithia-2-silacyclopent-4-ene.
  • 34
    • 0001580762 scopus 로고
    • Patai, S., Rappoport, Z., Eds.; Wiley: Chichester. UK
    • Bock, H.; Solouki, B. In The Chemistry of Organic Silicon Compounds: Patai, S., Rappoport, Z., Eds.; Wiley: Chichester. UK, 1989: Part 1, pp 555-563.
    • (1989) The Chemistry of Organic Silicon Compounds , Issue.PART 1 , pp. 555-563
    • Bock, H.1    Solouki, B.2
  • 42
    • 0343787877 scopus 로고
    • For use of photoelectron spectroscopy to probe the interaction of Si-Si σ-MOs with adjacent π-systems in tetrasila[2.2]paracyclophane, see: Gleiter, R.; Schäfer, W.; Krennrich, G.; Sakurai, H. J. Am. Chem. Soc. 1988, 110, 4117-4120.
    • (1988) J. Am. Chem. Soc. , vol.110 , pp. 4117-4120
    • Gleiter, R.1    Schäfer, W.2    Krennrich, G.3    Sakurai, H.4
  • 43
    • 33749528702 scopus 로고    scopus 로고
    • note
    • Since the time scale for PES ionization is much shorter than that for electrochemical oxidation, the correlation breaks down when there is significant molecular reorganization on removal of an electron. See ref 22 for examples.
  • 47
    • 33749525614 scopus 로고    scopus 로고
    • note
    • 2-S bond with the 3p lone pair orbital on the back sulfur atom drawn.
  • 48
    • 84985649732 scopus 로고
    • The four-membered ring in 3,3-dimethyl-2,2,4,4-tetraphenyl-1,3- thiasiletane is also planar: Strohmann, C. Chem. Ber. 1995, 128, 167-172.
    • (1995) Chem. Ber. , vol.128 , pp. 167-172
    • Strohmann, C.1
  • 49
    • 33749516242 scopus 로고    scopus 로고
    • note
    • 15b,16,27 In general, a linear correlation between the two measurements for the compounds reported in this paper has been found (manuscript in preparation).
  • 53
    • 33749520920 scopus 로고    scopus 로고
    • note
    • Nevertheless, direct comparison between 2a and 5a must be viewed with caution because of other differences in orbital interactions. For example, in 2a, the two Si-Si σ-orbitals in the Si-Si-Si moiety combine to form π-like orbitals.
  • 57
    • 33749509136 scopus 로고    scopus 로고
    • note
    • 16,31 The PES and fitting parameters of 6a are given in the Supporting Information. The ionization at 8.82 eV also seen in its PES is silicon-based as shown by intensity changes on going from He I to He II ionization sources.
  • 62
    • 33749510025 scopus 로고    scopus 로고
    • note
    • 45
  • 81
    • 33749522463 scopus 로고    scopus 로고
    • note
    • 23 for 5a are comparable, and second, the experimentally determined and computed ionization energies for 2a.b, 5a, 7a, and 8a are correlated.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.