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Volumn 18, Issue 20, 1999, Pages 4015-4026

Theoretical study of the structure, bonding nature, and reductive elimination reaction of Pd(XH3) (η3-C3H5) (PH3) (X = C, Si, Ge, Sn). Hypervalent behavior of group 14 elements

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EID: 0000976398     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om990296l     Document Type: Article
Times cited : (54)

References (70)
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    • 3 is very small (Sakaki, S.; Satoh, H.; Shono, H.; Ujino, U. Organometallics 1996, 15, 1713), Since the optimized geometry of PH3 deviates little from the experimental one used here, the frequency calculation could be carried out without any problem.
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    • Sakaki, S.1    Satoh, H.2    Shono, H.3    Ujino, U.4
  • 51
    • 3643117846 scopus 로고    scopus 로고
    • note
    • 3 bond energy.
  • 52
    • 3643065736 scopus 로고    scopus 로고
    • note
    • 3 between the distorted geometry taken in the TS and the equilibrium structure was calculated to be 52.5, 22.5, 17.3, and 9.6 kcal/mol for X = C, Si, Ge, and Sn, respectively. These are about 58%, 26%, 22%, and 14% of the C-C, C-Si, C-Ge, and C-Sn bond energies, respectively. Thus, the C-Si, C-Ge, and C-Sn bond formations are about 80% completed at the TS, while the C-C bond formation is not completed at all.
  • 53
    • 3643136548 scopus 로고    scopus 로고
    • note
    • 3 takes the nearest position to Pd as in Prd-C. The third is somewhat less stable than the first and second isomers, and therefore, it is not mentioned here. The energy difference between the first and the second minima is very small; the former is more stable than the latter by -0.2, 0.2, 0.5, and 0.1 kcal/ mol for X = C, Si, Ge, Sn, respectively, at the CCSD(T)/BS-II level, where the negative value represents that the former is less stable. The rotation barrier is calculated to be 4.5 kcal/mol for X = C and 4.0 kcal/ mol for X = Si with the MP2/BS-H method.
  • 54
    • 3643139751 scopus 로고    scopus 로고
    • note
    • 3 due to the C-Si, C-Ge, and C-Sn bonds being longer than the C-C bond.
  • 59
    • 85085633370 scopus 로고    scopus 로고
    • note
    • 42b
  • 62
    • 3643113690 scopus 로고    scopus 로고
    • note
    • 3 population is 0.532e by the present basis set, 0.531e by 6-311G*, and 0.526e by 6-311+G*.
  • 67
    • 3643060475 scopus 로고    scopus 로고
    • note
    • 3).
  • 68
    • 85085633949 scopus 로고    scopus 로고
    • note
    • 3).


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.