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Volumn 30, Issue 21, 2011, Pages 5815-5824

The nature of the silicon-oxygen bond

Author keywords

[No Author keywords available]

Indexed keywords

BENT'S RULE; BOND ANGLE; DONOR-ACCEPTORS; H-BONDING; HYPERCONJUGATION; HYPERCONJUGATIVE INTERACTIONS; NATURAL BOND ORBITAL;

EID: 80755130110     PISSN: 02767333     EISSN: 15206041     Source Type: Journal    
DOI: 10.1021/om200675d     Document Type: Article
Times cited : (146)

References (66)
  • 26
    • 0000097150 scopus 로고    scopus 로고
    • Natural bond orbital methods
    • Schleyer, P. v. R., Allinger, N. L., Clark, T., Gasteiger, J., Kollman, P. A., Schaefer, H. F., III, Schreiner, P. R., Eds.
    • Weinhold, F. Natural Bond Orbital Methods. In Encyclopedia of Computational Chemistry; Schleyer, P. v. R., Allinger, N. L., Clark, T., Gasteiger, J., Kollman, P. A., Schaefer, H. F., III, Schreiner, P. R., Eds.; 1998; Vol. 3, pp 1792-1811.
    • (1998) Encyclopedia of Computational Chemistry , vol.3 , pp. 1792-1811
    • Weinhold, F.1
  • 32
    • 80755166831 scopus 로고    scopus 로고
    • Ref 23, pp 220ff.
    • Ref , vol.23
  • 35
    • 80755166831 scopus 로고    scopus 로고
    • Ref 23, pp 593ff.
    • Ref , vol.23
  • 38
    • 0004025325 scopus 로고    scopus 로고
    • Theoretical Chemistry Institute, University of Wisconsin: Madison, WI
    • Weinhold, F. NBO 5.0 Program Manual; Theoretical Chemistry Institute, University of Wisconsin: Madison, WI, 2001; pp B-16ff; http://www.chem.wisc.edu/ ?nbo5/tut-del.htm.
    • (2001) NBO 5.0 Program Manual
    • Weinhold, F.1
  • 49
    • 80755157989 scopus 로고    scopus 로고
    • With regard to ethane-type barrier analysis, a referee has called our attention to a recent article [Mo, Y. Nat. Chem. 2011, 469, 76-79.
    • (2011) Nat. Chem. , vol.469 , pp. 76-79
    • Mo, Y.1
  • 51
    • 80755142359 scopus 로고    scopus 로고
    • in press; (DOI 1002/wcms.51); ref 46; ref 23
    • for original exposition of this viewpoint] with the remark that "...the NBO technique...is known for its overestimation of hyperconjugation energies, as the derivation of the Lewis wavefunction from the molecular wavefunction is non-optimal." To this we would reply that Mo's preferred BLW assessment is intrinsically based on the ambiguities of nonorthogonal orbitals, in which significant "overlap density" (not uniquely assignable to one center or another) makes the assessment of hyperconjugative charge "transfer" essentially subjective and arbitrary. In contrast, overlap-free NBO estimates of hyperconjugation energy, whether evaluated by complementary perturbative or $DEL-deletion techniques, have been demonstrated to correlate accurately with one another as well as with NBO-based weightings of the associated resonance structures [see, for example,.Glendening, E. D.; Landis, C. R.; Weinhold, F. Wiley Interdisciplinary Reviews: Computational Molecular Science (in press; DOI 1002/wcms.51); ref 46; ref 23, pp 622ff].
    • Wiley Interdisciplinary Reviews: Computational Molecular Science
    • Glendening, E.D.1    Landis, C.R.2    Weinhold, F.3
  • 52
    • 33847626622 scopus 로고    scopus 로고
    • These resonance weightings in turn exhibit close agreement with experimentally inferred values [see, for example., Kemnitz, C. R.; Loewen, M. J. J. Am. Chem. Soc. 2007, 129, 2521-2528], which precludes any significant "overestimation" of hyperconjugation energy or related structural effects. It should also be emphasized that the sum of all hyperconjugation energies, as defined with respect to the idealized NLS limit of eq 4b, is obtained from a rigorous variational expectation value (not a "nonoptimal" estimate), so any purported tendency to overestimate successive hyperconjugation energies must necessarily lead to (unobserved) violations of the variational theorem.
    • (2007) J. Am. Chem. Soc. , vol.129 , pp. 2521-2528
    • Kemnitz, C.R.1    Loewen, M.J.2
  • 55
    • 33947479158 scopus 로고
    • Bent, H. A. Chem. Rev. 1961, 61, 275-311. Ref 23, pp 138ff
    • (1961) Chem. Rev. , vol.61 , pp. 275-311
    • Bent, H.A.1
  • 56
    • 9844249529 scopus 로고
    • for early computational evidence of the strong dependence of XOH bending angle on electronegativity, see Schleyer, P. v. R. Pure Appl. Chem. 1987, 59, 1647.
    • (1987) Pure Appl. Chem. , vol.59 , pp. 1647
    • Schleyer, P.V.R.1
  • 57
    • 0003955397 scopus 로고
    • 2nd ed.; Oxford Univ. Press: London, Chapter 8
    • Coulson, C. A. Valence, 2nd ed.; Oxford Univ. Press: London, 1952; Chapter 8.
    • (1952) Valence
    • Coulson, C.A.1
  • 61
    • 0003600797 scopus 로고    scopus 로고
    • 5th ed. McGraw-Hill: Boston
    • Current textbook definitions of H-bonding (or, indeed, those of the past half-century) employ near-identical verbiage to express concurrence with the classical electrostatic "dipole-dipole" viewpoint, viz., "a special type of dipole-dipole force" [Silverberg, M. S. Chemistry: The Molecular Nature of Matter and Change, 5th ed.; McGraw-Hill: Boston, 2009; p 452]
    • (2009) Chemistry: The Molecular Nature of Matter and Change , pp. 452
    • Silverberg, M.S.1
  • 62
    • 0004229274 scopus 로고    scopus 로고
    • 6th ed. Houghton-Mifflin: Boston
    • "particularly strong dipolédipole forces" [Zumdahl, S. S. Chemical Principles, 6th ed.; Houghton-Mifflin: Boston, 2009; p 779]
    • (2009) Chemical Principles , pp. 779
    • Zumdahl, S.S.1
  • 65
    • 58249086571 scopus 로고    scopus 로고
    • 2nd ed.; Prentice-Hall: Boston
    • "a sort of super dipolédipole force" [ Tro, N. J., Chemistry: A Molecular Approach, 2nd ed.; Prentice-Hall: Boston, 2011; p 464], and the like.
    • (2011) Chemistry: A Molecular Approach , pp. 464
    • Tro, N.J.1


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