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Volumn 118, Issue 24, 1996, Pages 5745-5751

H2XO and (CH3)2XO compounds (X = C, Si, Ge, Sn, Pb): Double bonds vs carbene-flike structures - Can the metal compounds exist at all?

Author keywords

[No Author keywords available]

Indexed keywords

METAL COMPLEX;

EID: 0030017686     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja953846p     Document Type: Article
Times cited : (111)

References (93)
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    • (1986) J. Organomet. Chem. , vol.306 , pp. 9
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  • 33
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    • Elschenbroich, C.; Salzer, A. Organomelallics - A Concise Introduction; VCH: Weinheim, 1989; pp 95-146. For recent examples, see: (a) Glowacki, A.; Huber, F.; Preut, H. J. Organomet. Chem. 1986, 306, 9. (b) Blaschette, A.; Hamann, T.; Michalides, A.; Jones, P. G. J. Organomet. Chem. 1993, 456, 49. (c) Blaschette, A.; Wieland, E.; Jones, P. G.; Hippel, I. J. Organomet. Chem. 1993, 445, 55.
    • (1993) J. Organomet. Chem. , vol.456 , pp. 49
    • Blaschette, A.1    Hamann, T.2    Michalides, A.3    Jones, P.G.4
  • 34
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    • Elschenbroich, C.; Salzer, A. Organomelallics - A Concise Introduction; VCH: Weinheim, 1989; pp 95-146. For recent examples, see: (a) Glowacki, A.; Huber, F.; Preut, H. J. Organomet. Chem. 1986, 306, 9. (b) Blaschette, A.; Hamann, T.; Michalides, A.; Jones, P. G. J. Organomet. Chem. 1993, 456, 49. (c) Blaschette, A.; Wieland, E.; Jones, P. G.; Hippel, I. J. Organomet. Chem. 1993, 445, 55.
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    • Blaschette, A.1    Wieland, E.2    Jones, P.G.3    Hippel, I.4
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    • Kutzelnigg analyzed the σ and p bonding of main group element compounds in detail in a landmark review: Kutzelnigg, W. Angew. Chem., Int. Ed. Engl. 1984, 23, 272.
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    • Elsevier: New York
    • Bergner, A.; Dolg, M.; Küchle, W.; Stoll, H.; Preuss, H. Mol. Phys. 1993, 80, 1431. d-Polarization Functions: Gaussian Basis Sets for Molecular Calculations; Huzinaga, S., Ed.; Elsevier: New York, 1984.
    • (1984) Gaussian Basis Sets for Molecular Calculations
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    • note
    • For systems of this size the MP2 optimizations are about 1.5 times slower than the corresponding Becke3LYP computations (HP735 workstation). However, the MP4SDTQ and CCSD(T) single point calculations are 20 to 75 times more expensive than similar DFT computations with the same basis sets.
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    • note
    • 2XO isomers change by 0-3 kcal/mol (Tables 1 and 2); this has no influence on the trends or the interpretation. Therefore, the ZPE was not included in the calculation of the reaction energies 1 and 2.
  • 77
    • 0001549173 scopus 로고
    • 2X=O/trans-HXOH energy differences are (in kcal/mol. no ZPE correction, Table 1): C 52.60, Si -3.11, Ge -31.59, Sn -51.49, nonrelativistic Pb -53.43, Pb -72.41. See also: Grev, R. S.; Schaefer III, H. F. Organometallics 1992, 11, 3489.
    • (1992) Organometallics , vol.11 , pp. 3489
    • Grev, R.S.1    Schaefer III, H.F.2
  • 80
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    • 2Ge=O: Khabashesku, V. N.; Kerzina, Z. A.; Boganov, S. E.; Nefedov, O. M. In IX International Symposium on Organosilicon Chemistry, Edinburgh, 1990; Abst. P. 8.25.
    • (1986) J. Am. Chem. Soc. , vol.108 , pp. 8118
    • Withnall, R.1    Andrews, L.2
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    • 8944223937 scopus 로고    scopus 로고
    • note
    • A referee suggested that the X=O π bond energies might be evaluated from the trimerization energies. Although this is an interesting suggestion, the energies obtained by this procedure (C=O: 72 kcal/mol, Si=O: 44 kcal/mol) strongly deviate from π bond estimates obtained from other, more general procedures (C=O: 98 kcal/mol, Si=O: 55 kcal/mol), see ref 16b. Obviously, the involvement of the σ system (Table 3) is not negligible.
  • 86
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    • Electronegativity
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    • (b) Electronegativity. In Structure and Bonding; Sen, K. D., Ed.; Springer Verlag: Berlin, 1987; Vol. 66.
    • (1987) Structure and Bonding , vol.66
    • Sen, K.D.1
  • 90
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    • note
    • As Kutzelnigg pointed out in ref 15, π bonds formed by pure heavy element p orbitals are far less favorable than σ bonds with s contributions. However, an s lone pair fas in the divalent isomers) is even more favorable, since the electrons are not shared with other atoms.
  • 91
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    • 1.30). The NPA Pb-R bond orders increase (Table 4), while the Pb-R distances decrease (R = H: 3-7 pm Table 3), see: Schwerdtfeger, P.; Silberbach, M.; Miehlich, B. J. Chem. Phys. 1989, 90, 762.
    • (1989) J. Chem. Phys. , vol.90 , pp. 762
    • Schwerdtfeger, P.1    Silberbach, M.2    Miehlich, B.3


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