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Volumn 114, Issue 26, 2010, Pages 7213-7222

Tuning σ-holes: Charge redistribution in the heavy (Group 14) analogues of simple and mixed halomethanes can impose strong propensities for halogen bonding

Author keywords

[No Author keywords available]

Indexed keywords

CHARGE REDISTRIBUTION; HALOGEN BONDING; HALOGEN BONDS; HALOMETHANES; INORGANIC HALIDES; INTERMOLECULAR INTERACTIONS; LEWIS BASIS; ORGANIC MOLECULES; RELATIVE STRENGTH;

EID: 77954321833     PISSN: 10895639     EISSN: 15205215     Source Type: Journal    
DOI: 10.1021/jp102856v     Document Type: Article
Times cited : (40)

References (75)
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    • 2nd ed.; Elsevier Butterworth-Heinemann: Oxford,. See Chapter 10, in particular, section 10.2.4, p. 373ff for some of the differences in the chemical reactivity of the elements and the (in)stability of some compounds. See also the tables on pp 372 and 373
    • Greenwood, N. N.; Earnshaw, A. Chemistry of the Elements, 2nd ed.; Elsevier Butterworth-Heinemann: Oxford, 2005. See Chapter 10, in particular, section 10.2.4, p. 373ff for some of the differences in the chemical reactivity of the elements and the (in)stability of some compounds. See also the tables on pp 372 and 373.
    • (2005) Chemistry of the Elements
    • Greenwood, N.N.1    Earnshaw, A.2
  • 2
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    • See, for example, p 339; section 10.3.1 pp 374-375 in ref 1
    • See, for example, p 339; section 10.3.1 pp 374-375 in ref 1.
  • 4
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    • Section 9.3.3, pp 340-342 in ref 1
    • Section 9.3.3, pp 340-342 in ref 1.
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    • and 10.3.2, pp 381-382, 385 in ref 1
    • See sections 10.3.1, pp 374 - 375, and 10.3.2, pp 381-382, 385 in ref 1.
    • See Sections 10.3.1 , pp. 374-375
  • 9
    • 77954317607 scopus 로고    scopus 로고
    • note
    • See refs 6 and 7. We determined that the lengthening of the M-X bond as n increases is caused by a competition between the M-X attraction and the X-X repulsions around the small carbon center for the large Cl and Br terminal atoms.
  • 15
    • 77954337065 scopus 로고    scopus 로고
    • note
    • In a halogen bond (R-X-Y-R′), the halide, X, is bonded to some moderately to very electron withdrawing group R. The group electronegativity of R determines how substantial the shift in the electron density along the bond axis - away from X and toward R - will be.
  • 19
    • 77954323868 scopus 로고    scopus 로고
    • note
    • In ref 11, Politzer et al. suggests that the term "halogen bond" was first used in ref 15a. We have not been able to find any earlier use of the term.
  • 23
  • 35
    • 77954319400 scopus 로고    scopus 로고
    • note
    • We use the term "strength" instead of electrophilicity to refer to the positive electrostatic potential (ESP) within the σ-hole. The σ-hole gets stronger as the ESP gets more positive.
  • 36
    • 84865658500 scopus 로고    scopus 로고
    • An Overview of σ-Hole Bonding, an Important and Widely-Occurring Noncovalent Interaction. in
    • Leszczynski, J.,; Shukla, M. K. Eds.; Springer: Heidelberg,; Ch. 6
    • Politzer, P.; Murray, J. S. An Overview of σ-Hole Bonding, an Important and Widely-Occurring Noncovalent Interaction. In Practical Aspects of Computational Chemistry Methods, Concepts, and Applications; Leszczynski, J.,; Shukla, M. K. Eds.; Springer: Heidelberg, 2009; Ch. 6.
    • (2009) Practical Aspects of Computational Chemistry Methods, Concepts, and Applications
    • Politzer, P.1    Murray, J.S.2
  • 41
    • 47249165244 scopus 로고    scopus 로고
    • See also refs 5 - 13 therein. As this reference emphasizes, halogen bonding depends on the variation in the charge distribution (hence the magnitude and sign of the electrostatic potential) across the surface of X atoms in molecules. This critical level of detail is sacrificed in point charge models
    • Politzer, P.; Murray, J. S.; Concha, M. C. J. Mol. Model. 2008, 14, 659 See also refs 5 - 13 therein. As this reference emphasizes, halogen bonding depends on the variation in the charge distribution (hence the magnitude and sign of the electrostatic potential) across the surface of X atoms in molecules. This critical level of detail is sacrificed in point charge models
    • (2008) J. Mol. Model. , vol.14 , pp. 659
    • Politzer, P.1    Murray, J.S.2    Concha, M.C.3
  • 42
    • 77954319873 scopus 로고    scopus 로고
    • note
    • Even if X in the acid/base pair R-X-Y-R′ has a noticeable local σ-hole (outside the bonding region; see Figure 1) it is still possible for X to have a net (global) negative charge if, in the bonding region, the R → X charge transfer is significant. Now, since Y is necessarily an electron-rich site, it would have a net negative change as well. Thus, a simple point charge model would predict, incorrectly, that the interaction between X and Y is always repulsive, independent of the R-X-Y bond angle. See ref 32.
  • 47
    • 0347151609 scopus 로고    scopus 로고
    • (for Sn and Pb)
    • Peterson, K. A. J. Chem. Phys. 2003, 119, 11099 (for Sn and Pb)
    • (2003) J. Chem. Phys. , vol.119 , pp. 11099
    • Peterson, K.A.1
  • 48
    • 33846365941 scopus 로고    scopus 로고
    • (for I). The correlation consistent triple-zeta (cc-pVTZ-pp) basis sets used are from the website of the Institute for Theoretical Chemistry at the University of Stuttgart
    • Peterson, K. A.; Shepler, B. C.; Figgen, D.; Stoll, H. J. Phys. Chem. A 2006, 110, 13877 (for I). The correlation consistent triple-zeta (cc-pVTZ-pp) basis sets used are from the website of the Institute for Theoretical Chemistry at the University of Stuttgart: http://www.theochem.uni-stuttgart.de/ pseudopotentials/clickpse.en.html
    • (2006) J. Phys. Chem. A , vol.110 , pp. 13877
    • Peterson, K.A.1    Shepler, B.C.2    Figgen, D.3    Stoll, H.4
  • 50
    • 77954346125 scopus 로고    scopus 로고
    • note
    • The GaussView (3.0 and 4.1) graphics program has been used to plot the representations of the electrostatic potentials in this report.
  • 56
    • 77954337841 scopus 로고    scopus 로고
    • note
    • Results obtained at the MP2 level for the halomethanes, and their silicon and germanium analogues have been presented and discussed in detail in parts 1 and 2 of the series. Small differences have been observed between the geometrical and other MP2(full) data from this work for C, Si, and Ge (shown in the supporting information) and the data available in the preceding papers in the series.
  • 57
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    • See ref 43
    • See ref 43.
  • 59
    • 77954339084 scopus 로고    scopus 로고
    • note
    • In contrast to the less expensive MP2 method, the MP2(full) method takes all the core electrons into account in assessing the contributions of the doubly excited state to the total energy of the system.
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    • note
    • n (X = F, Cl, and Br). See ref 8.
  • 61
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    • note
    • The relatively smaller changes in the atomic radii after silicon are explained by the well known d-orbital and lanthanide contractions (after period three, and from periods five (Sn) to six (Pb), respectively). For Pb, relativistic effects are responsible for a contraction of the valence s and p orbitals, as well.
  • 67
    • 77954331453 scopus 로고    scopus 로고
    • note
    • Although atomic electronegativities are not quantum mechanical observables, they remain indispensible and chemically meaningful tools for discussions of the charge distributions in molecules. For a detailed discussion of a relationship between atomic polarizabilities and Pauling electronegativities. See
  • 69
    • 77954335621 scopus 로고    scopus 로고
    • note
    • Pb = 3.90 eV; Table 1).


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.