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Volumn 82, Issue 6, 2009, Pages 712-722

How are non-bonded G. . .Z (Z = O, S, and Se) distances at benzene 1,2-, naphthalene 1,8-, and anthracene 1,8,9-positions controlled? An approach to causality in weak interactions

Author keywords

[No Author keywords available]

Indexed keywords

CLOSED SHELLS; REPULSIVE INTERACTIONS; WEAK INTERACTIONS;

EID: 67651056128     PISSN: 00092673     EISSN: 13480634     Source Type: Journal    
DOI: 10.1246/bcsj.82.712     Document Type: Article
Times cited : (8)

References (63)
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    • Let us consider a molecular complex (MC) formation from a selenide with iodine, O(CH2CH2)2Se£II, as an example.3 The attractive interaction between Se and I2 and the formation of the Se£I bond correspond to cause 1 and result A, respectively. The Se£I distance should be shorter than the sum of van der Waals radii of the atoms but longer than the sum of covalent radii of the atoms: the observed r(Se£I, rvdW(Se, rvdW(I, and rCO(Se, rCO(I) are 2.755, 4.15, and 2.50¡, respectively.3 Therefore, result A is well explained by cause 1. Result A derives spontaneously from cause-S1, which produces some phenomena. The II distance in the adduct must be smaller than that of the I2 molecule, which should be result-R2. The r(II) in the adduct and I2 itself are 2.956 and 2.666¡,3 respectively. Result-R2 is also well explained by cause A
    • Let us consider a molecular complex (MC) formation from a selenide with iodine, O(CH2CH2)2Se£II, as an example.3 The attractive interaction between Se and I2 and the formation of the Se£I bond correspond to cause 1 and result A, respectively. The Se£I distance should be shorter than the sum of van der Waals radii of the atoms but longer than the sum of covalent radii of the atoms: the observed r(Se£I), rvdW(Se) + rvdW(I), and rCO(Se) + rCO(I) are 2.755, 4.15, and 2.50¡, respectively.3 Therefore, result A is well explained by cause 1. Result A derives spontaneously from cause-S1, which produces some phenomena. The II distance in the adduct must be smaller than that of the I2 molecule, which should be result-R2. The r(II) in the adduct and I2 itself are 2.956 and 2.666¡,3 respectively. Result-R2 is also well explained by cause A.
  • 6
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    • Interactions are defined by the AIM (Atoms-in-Molecules) functions at bond critical points (BCPs: rc).41,42 They are called closed-shell (CS) interactions when the Laplacian of electron densities at rc (|μb(rc)) are positive (|μb(rc) > 0) where μb(rc) are locally depleted relative to the average distribution around rc. On the other hand, μb(rc) are locally concentrated relative to the average distribution around bond critical points if |μb(rc) < 0. Interactions in this region are called shared-shell (SS) interactions. Interactions of |μb(rc) > 0 are discussed here.
    • Interactions are defined by the AIM (Atoms-in-Molecules) functions at bond critical points (BCPs: rc).41,42 They are called closed-shell (CS) interactions when the Laplacian of electron densities at rc (|μb(rc)) are positive (|μb(rc) > 0) where μb(rc) are locally depleted relative to the average distribution around rc. On the other hand, μb(rc) are locally concentrated relative to the average distribution around bond critical points if |μb(rc) < 0. Interactions in this region are called shared-shell (SS) interactions. Interactions of |μb(rc) > 0 are discussed here.
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    • The formation of iodine adducts with selenides is a typical example: see: O. Hassel, K. O. Strømme, Acta Chem. Scand. 1959, 13, 1775; O. Hassel, J. Hvoslef, Acta Chem. Scand. 1954, 8, 873.
    • The formation of iodine adducts with selenides is a typical example: see: O. Hassel, K. O. Strømme, Acta Chem. Scand. 1959, 13, 1775; O. Hassel, J. Hvoslef, Acta Chem. Scand. 1954, 8, 873.
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    • Extended hypervalent 4c6e interactions of the G£ZZ£ G type are also observed in the linear S4 and Se4 atoms.5a5d, 5g
    • Extended hypervalent 4c6e interactions of the G£ZZ£ G type are also observed in the linear S4 and Se4 atoms.5a5d, 5g
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    • Although CC (C2) is the desirable structure for 2 (SeMe, SeMe, the structure gives one negative (imaginary) frequency for an internal motion after the frequency analysis. Instead, 2 (SeMe, SeMe, CC: C1, which is very close to 2 SeMe, SeMe, CC: C2, gave positive frequencies for all internal motions by the frequency analysis
    • Although CC (C2) is the desirable structure for 2 (SeMe, SeMe), the structure gives one negative (imaginary) frequency for an internal motion after the frequency analysis. Instead, 2 (SeMe, SeMe) (CC: C1), which is very close to 2 (SeMe, SeMe) (CC: C2), gave positive frequencies for all internal motions by the frequency analysis.
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    • See the SI for the results of B3LYP calculations.
    • See the SI for the results of B3LYP calculations.
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    • Similarly, three types of fine structures are observed for 1-methylselanyl-8-(p-substituted phenylselanyl)naphthalenes [1-MeSe-8-(p-YC6H4Se)C10H6, 6 (SeMe, SeAr): Y =H (a), OMe (b), and Cl (c)]. Non-bonded r(Se£Se) distances in 6a (SeMe, SeAr), 6b (SeMe, SeAr), and 6c (SeMe, SeAr) are reported to be 3.070¡ [the average between 3.048(1) and 3.091(1)¡], 3.0951(8), and 3.1239(7)¡, respectively.5e The structures are CC, pseudo-AB, and pure-AB, respectively. The r(Se£Se) value becomes larger in an order of CC < pseudo-AB < pure-AB.
    • Similarly, three types of fine structures are observed for 1-methylselanyl-8-(p-substituted phenylselanyl)naphthalenes [1-MeSe-8-(p-YC6H4Se)C10H6, 6 (SeMe, SeAr): Y =H (a), OMe (b), and Cl (c)]. Non-bonded r(Se£Se) distances in 6a (SeMe, SeAr), 6b (SeMe, SeAr), and 6c (SeMe, SeAr) are reported to be 3.070¡ [the average between 3.048(1) and 3.091(1)¡], 3.0951(8), and 3.1239(7)¡, respectively.5e The structures are CC, pseudo-AB, and pure-AB, respectively. The r(Se£Se) value becomes larger in an order of CC < pseudo-AB < pure-AB.
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    • The structure of III was determined by means of X-ray crystallographic analysis:, unpublished results
    • The structure of III was determined by means of X-ray crystallographic analysis: W. Nakanishi, S. Hayashi, unpublished results.
    • Nakanishi, W.1    Hayashi, S.2
  • 50
    • 67651047672 scopus 로고    scopus 로고
    • The values for I (BB) and IV (AA) are averaged values. And the observed values are from p-chlorophenyl group in place of phenyl groups.
    • The values for I (BB) and IV (AA) are averaged values. And the observed values are from p-chlorophenyl group in place of phenyl groups.


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