Structural effects of carbon monoxide coordination to carbon centers, π and σ bindings in aliphatic acyl versus aromatic aroyl cations

New Journal of Chemistry

Volumn 28, Issue 12, 2004, Pages 1568-1574

  Davlieva, Milya G ^a   Lindeman, Sergey V ^a   Neretin, Ivan S ^a   Kochi, Jay K ^a  

^a University of Houston   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALIPHATIC COMPOUND; ALKYL GROUP; AROMATIC COMPOUND; CARBON; CARBON MONOXIDE; CARBONYL DERIVATIVE; CATION; COORDINATION COMPOUND; FLUORINE DERIVATIVE; METHYL GROUP; OXOCARBONIUM ION; PHENYL GROUP; UNCLASSIFIED DRUG;

ARTICLE; CHEMICAL BINDING; CHEMICAL BOND; CHEMICAL INTERACTION; CHEMICAL REACTION; CHEMICAL STRUCTURE; CRYSTAL STRUCTURE; INFRARED SPECTROSCOPY; PARAMETER; PRIORITY JOURNAL; SOLID STATE; STRUCTURE ANALYSIS; SYNTHESIS; TEMPERATURE DEPENDENCE; WETTABILITY; X RAY CRYSTALLOGRAPHY;

EID: 11244258961     PISSN: 11440546     EISSN: None     Source Type: Journal    
DOI: 10.1039/b407654k     Document Type: Article

References (44)

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10. The isolation and X-ray crystallography of the resultant oxocarbonium hydrates (identified as α,α-dihydroxycarbonium ions) will be reported separately.
11. - salt (earlier studied by Le Carpentier and Weiss8a) was not quite successful because of the intrinsic racemic twinning of these crystals.
12. (a) J.-M. Le Carpentier and R. Weiss, Acta Crystallogr., Sect. B, 1972, 28, 1421;
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16. (b) See also: S. V. Lindeman and J. K. Kochi, Cryst. Growth Design, 2004, 4, 563. Note that the arenediazonium cations are isoelectronic to aroylium cations and their salts are likely to be isostructural.
17. (a) For a lucid presentation of this electroneutrality principle, see: F. A. Cotton and G. Wilkinson. Advanced Inorganic Chemistry, Wiley-Interscience, NY, 5th edn., 1988, p. 57;
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19. n Tables 3 and 4 (vide infra).
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21. 1 = 1.48 Å and K = 0.50, which includes the correction for the change in covalent radius with hybridization. See, for example: S. M. Hubig, S. V. Lindeman and J. K. Kochi, Coord. Chem. Revs., 2000, 200, 831. The calculated bond orders are presented in the Table 3 with esds in parentheses.
22. + , and the deficit of 0.3 e can be attributed to the diminished hyperconjugation of the i-propyl group,19 this deficiency being made up by its increased σ bonding characteristics21.
23. Fig. 1and Fig. 2 locate the center of positive charge on the central (carbonyl) carbon atom.
24. F. H. Allen, O. Kennard, D. G. Watson, L. Brammer, A. G. Orpen and R. Taylor, J. Chem. Soc., Perkin Trans. 2, 1987, S1.
25. CO = 1.07 Å in an authentic (C ≡ O) triple bond18;
26. + cation greatly diminishes the efficiency of the hyperconjugation.
27. Considering the covalent radii of carbon and oxygen to be constant, extrapolation from standard values16 1.54 and 1.43 Å for single bonds C-C and C-O, respectively, 1.32 and 1.21 Å for double bonds C=C and C=O (i.e. -0.22 Å each), respectively, and 1.18 Å for triple bond C ≡ C, gives 1.07 Å for C ≡ O (i.e. -0.14 and -0.36 Å each, relative to the corresponding double and single bonds, respectively).
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31. For example, see the inductive parameters for the Hammett and Taft linear free-energy correlations in: T. H. Lowry, and K. S. Richardson. Mechanism and Theory in Organic Chemistry, Harper-Row, New York, 2nd edn., 1981, p. 137.
32. The decreasing strength of the carbonyl bond in acyl cations derives from the increased interaction in the order: i-Pr > Et > Me of the σ orbital of the alkyl substituent with the antibonding σ* orbital of carbonyl group as previously described by Strauss et al.2.
33. (a) Such a quinonoidal distortion is shown by the shortening of the endocyclic d (1.378 Å) as compared with c bonds (1.405 Å) and e bonds (1.408 Å) in Table 2;
34. (b) For discussion of this type of quinonoidal distortion in cations, see: S. V. Lindeman. S. V. Rosokha, D. Sun and J. K. Kochi, J. Am. Chem. Soc., 2002, 124, 843;
35. (c) Compare Le Carpentier et al., in refs. 4 and 8.
36. (a) Quinonoidal distortion with the d bond of 1.368 Å;
37. -1, from monomethyl and trimethyl to pentamethyl analogs;
38. (c) Quinonoidal distortion with the shortest d bond = 1.360 Å.
39. + (vide supra).
40. However, the fluorine substituent also has a noticeable mesomeric effect on the benzenoid substituent that exhibits a rather pronounced quinonoidal distortion with the d bond of 1.366 Å.
41. 1 = 1.455 Å and K = 0.50.
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