Charge-shift bonding in group IVB halides: A valence bond study of MH3- Cl (M = C, Si, Ge, Sn, Pb) molecules

Journal of the American Chemical Society

Volumn 121, Issue 4, 1999, Pages 822-834

  Shurki, Avital ^a   Hiberty, Philippe C ^b   Shaik, Sason ^a  

^a HEBREW UNIVERSITY OF JERUSALEM   (Israel)

^b UNIVERSITÉ PARIS SACLAY   (France)

Author keywords

[No Author keywords available]

Indexed keywords

CARBON; GERMANIUM; HALIDE; LEAD; SILICON; TIN;

ARTICLE; CHEMICAL STRUCTURE; IONIC STRENGTH; MOLECULAR INTERACTION; MOLECULAR STABILITY;

EID: 0033518599     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja982218f     Document Type: Article

References (101)

1. (a) Lewis, G. N. J. Am. Chem. Soc. 1916, 38, 762.
2. (b) Langmuir, I. J. Am. Chem. Soc. 1919, 41, 868, 1543.
3. Pauling, L. The Nature of the Chemical Bond, 3rd ed.; Cornell University Press: Ithaca, NY, 1960.
4. Heitler, W.; London, H. F. Physik 1927, 44, 455.
5. Shaik, S. S. In New Theoretical Concepts for Understanding Organic Reactions; Bertrán, J., Csizmadia, I. G., Eds.; Kluwer Academic Publishers: Dordrecht, The Netherland, 1989; Vol. C267.
6. (a) Sini, G.; Maitre, P.; Hiberty, P. C.; Shaik, S. S. J. Mol. Struct. (THEOCHEM) 1991, 229, 163.
7. (b) Shaik, S.; Maitre, P.; Sini, G.; Hiberty, P. C. J. Am. Chem. Soc. 1992, 114, 7861.
8. (c) Lauvergnat, D.; Hiberty, P. C.; Danovich, D.; Shaik, S. J. Phys. Chem. 1996, 100, 5715.
9. (d) Shaik, S. S. In Molecules in Natural Science and Medicine, Maksic, Z. B., Eckert-Maksic, M., Eds.; Ellis-Horwood: New York, 1991; Chapter 12.
10. (e) Shaik, S.; Shurki, A. Angew. Chem., in press.
11. Basch, H.; Aped, P. Hoz, S. Mol. Phys. 1996, 89, 331.
12. ion), while ignoring completely the charge-shift resonance between the ionic and covalent forms.
13. Verbeek, J.; Langenberg, J. H.; Byrman, C. P.; Van Lenthe, J. H. TURTLE-ab-initio VB/VBSCF/VBCI program, Theoretical Chemistry Group, Debye Institute, University of Utrecht, 1993.
14. Kutzelnigg, W. Angew. Chem. 1984, 96, 262; Angew. Chem., Int. Ed. Engl. 1984, 23, 272.
15. Kutzelnigg, W. Angew. Chem. 1984, 96, 262; Angew. Chem., Int. Ed. Engl. 1984, 23, 272.
16. See for example recent extensive reviews: (a) Patai, S.; Rappoport, Z. The Chemistry of organic Silicon Compounds; Wiley and Sons: Chichester, England, 1989; Vols. 1 and 2. (b) Patai, S. The Chemistry of organic Germanium. Tin and Lead Compounds; Wiley and Sons: Chichester, England, 1995.
17. See for example recent extensive reviews: (a) Patai, S.; Rappoport, Z. The Chemistry of organic Silicon Compounds; Wiley and Sons: Chichester, England, 1989; Vols. 1 and 2. (b) Patai, S. The Chemistry of organic Germanium. Tin and Lead Compounds; Wiley and Sons: Chichester, England, 1995.
18. Apeloig, Y. Theoretical Aspects of Organosilicon Compounds. Vol. 1, Chapter 2 in ref 10a.
19. (a) Luke, B. T.; Pople, J. A.; Krogh-jespersen, M.-B.; Apeloig, Y.; Chandrasekhar, J.; Schleyer, P. v. R. J. Am. Chem. Soc. 1986, 108, 260.
20. 3M-Cl (M = C, Si, Ge, Sn) using DFT: Bickelhaupt, F. M.; Ziegler, T.; Schleyer, P. v. R. Organometallics 1996, 15, 1477.
21. Laube, T. Acc. Chem. Res. 1995, 28, 399.
22. Prakash, G. K. S.; Keyaniyan, S.; Anisrfeld, S. K. R.; Heiliger, L.; Olah, G. A.; Stevens, R. C.; Choi, H.-K.; Bau, R. J. Am. Chem. Soc. 1987, 109, 5123.
23. Gomes de Mesquita, A. H.; MacGillavry, C. H.; Eriks, K. Acta Crystallogr. 1965, 18, 437.
24. (a) Gronert, S.; Glaser, R.; Streitwieser, A., Jr. J. Am. Chem. Soc. 1989, 111, 3111.
25. (b) Reed, A. E.; Weinstock, R. B.; Weinhold, F. J. Chem. Phys. 1985, 83, 735.
26. (c) Wiberg, K. B.; Wendolowski, J. J. J. Phys. Chem. 1984, 88, 586.
27. (a) Apeloig, Y.; Stanger, A. J. Am. Chem. Soc. 1987, 109, 272.
28. (b) Apeloig, Y. Stud. Org. Chem. 1987, 31, 33.
29. (a) Lambert, J. B.; Kania, L.; Zhang, S. Chem. Rev. 1995, 95, 1191
30. (b) Schleyer, P. v. R. Science 1997, 275, 39.
31. (a) Schleyer, P. v. R.; Buzek, P.; Müller, T.; Apeloig, Y.; Siehl, H.-U. Angew. Chem. 1993, 105, 1558; Angew. Chem., Int. Ed. Engl. 1993, 32, 1471.
32. (a) Schleyer, P. v. R.; Buzek, P.; Müller, T.; Apeloig, Y.; Siehl, H.-U. Angew. Chem. 1993, 105, 1558; Angew. Chem., Int. Ed. Engl. 1993, 32, 1471.
33. (b) Steinberger, H.-U.; Müller, T.; Auner, N.; Maerker, C.; Schleyer, P. v. R. Angew. Chem. 1997, 109, 667; Angew. Chem., Int. Ed. Engl. 1997, 36, 626.
34. (b) Steinberger, H.-U.; Müller, T.; Auner, N.; Maerker, C.; Schleyer, P. v. R. Angew. Chem. 1997, 109, 667; Angew. Chem., Int. Ed. Engl. 1997, 36, 626.
35. Xie, Z.; Bau, R.; Benesi, A.; Reed, C. A. Organometamllics 1995, 14, 3933.
36. Lambert, J. B.; Zhao, Y. Angew. Chem. 1997, 109, 389; Angew. Chem., Int. Ed. Engl. 1997, 36, 400.
37. Lambert, J. B.; Zhao, Y. Angew. Chem. 1997, 109, 389; Angew. Chem., Int. Ed. Engl. 1997, 36, 400.
38. (a) See, Cremer, D.; Olsson, L.; Reichel, F.; Kraka, E. Isr. J. Chem. 1993, 33, 369.
39. (b) See however: Sekiguchi, A.; Tsukamoto, M.; Ichinohe, M. Science 1997, 275, 60.
40. (c) Jemmis, E. D.; Srinivas, G. N.; Leszcynski, J.; Kapp, J.; Korkin, A. A.; Schleyer, P. v. R. J. Am. Chem. Soc. 1995, 117, 11361.
41. (a) Albright, T. A.; Hoffman, P.; Rossi, A. R. Naturforsch. 1980, 35b, 343.
42. (b) Sheldriek, W. S. Chapter 3 in ref 10a.
43. Basch, H.; Hoz, T. Chapter 1 in ref 10b.
44. Basch, H. Inorg. Chim. Acta 1996, 252, 265.
45. Mackay, K. M. Chapter 2 in ref 10b.
46. Reed, A. E.; Schleyer, P. v. R. J. Am. Chem. Soc. 1990, 112, 1434.
47. Coulson, C. A. Nature 1969, 221, 1106.
48. (a) Pyykkö, P. Chem. Rev. 1988, 88, 563.
49. (b) Pyykko, P. J. Chem. Res. (S) 1979, 380.
50. Rendell, A. P.; Lee, T. J. J. Chem. Phys. 1994, 101, 400.
51. For CCD and CCSD(T) implemented in Gaussian 94 see: (a) Pople, J. A.; Krishnan, R.; Schlegel, H. B.; Binkley, J. S. Int. J. Quantum Chem. 1978, XIV, 545. (b) Pople, J. A.; Head-Gordon, M.; Raghavachari, K. J. Chem. Phys. 1987, 87, 5968.
52. For CCD and CCSD(T) implemented in Gaussian 94 see: (a) Pople, J. A.; Krishnan, R.; Schlegel, H. B.; Binkley, J. S. Int. J. Quantum Chem. 1978, XIV, 545. (b) Pople, J. A.; Head-Gordon, M.; Raghavachari, K. J. Chem. Phys. 1987, 87, 5968.
53. Gaussian 94, Revision D.4: Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Gill, P. M. W.; Johnson, B. G.; Robb, M. A.; Cheeseman, J. R.; Keith, T.; Petersson, G. A.; Montgomery, J. A.; Raghavachari, K.; Al-Laham, M. A.; Zakrzewski, V. G.; Ortiz, J. V.; Foresman, J. B.; Cioslowski, J.; Stefanov, B. B.; Nanayakkara, A.; Challacombe, M.; Peng, C. Y.; Ayala, P. Y.; Chen, W.; Wong, M. W.; Andres, J. L.; Replogle, E. S.; Gomperts, R.; Martin, R. L.; Fox, D. J.; Binkley, J. S.; Defrees, D. J.; Baker, J.; Stewart, J. P.; Head-Gordon, M.; Gonzalez, C.; Pople, J. A., Gaussian, Inc., Pittsburgh, PA, 1995.
54. (a) Grein, F.; Chang, T. C. Chem. Phys. Lett. 1971, 12, 44.
55. (b) Banerjee, A.; Grein, F. Int. J. Quantum Chem. 1976, 10, 123.
56. (c) Levy, B.; Berthier, G. Int. J. Quantum Chem. 1968, 2, 307.
57. Taking matters to an extreme situation, a single one-center expansion can be formally exact in an infinite basis set, but the wave function would not be interpretable in VB terms.
58. (a) For first-row elements it uses D95: Dunning, Jr., T. H.; Hay, P. J. In Modern Theoretical Chemistry; Schaefer; H. F., III, Ed.; Plenum: New York, 1976; p 1. For higher row elements (Na-Bi) it uses Los-Alamos ECP plus DZ: Hay, P. J.; Wadt, W. R. J. Chem. Phys. 1985, 82, 270, 284, 299.
59. (a) For first-row elements it uses D95: Dunning, Jr., T. H.; Hay, P. J. In Modern Theoretical Chemistry; Schaefer; H. F., III, Ed.; Plenum: New York, 1976; p 1. For higher row elements (Na-Bi) it uses Los-Alamos ECP plus DZ: Hay, P. J.; Wadt, W. R. J. Chem. Phys. 1985, 82, 270, 284, 299.
60. (b) For C, Si, Ge, Sn, and Cl, see: Bergner, A.; Dolg, M.; Kuechle, W.; Stoll, H.; Preuss, H. Mol. Phys. 1993, 80, 1431.
61. Bobrowicz, F. W.; Goddard, W. A., III. In Modern Theoretical Chemistry: Methods of Electronic Structure Theory, Schaefer, H. F., III, Ed.; Plenum: New York, 1977; Vol. 3, p 79.
62. (a) Cooper, D. L.; Gerratt, J.; Raimondi, M. Adv. Chem. Phys. 1987, 69, 319.
63. (b) Cooper, D. L.; Gerratt, J.; Raimondi, M. Int. Rev. Phys. Chem. 1988, 7, 59.
64. (c) Gerratt, J.; Cooper, D. L.; Raimondi, M. In Valence Bond Theory and Chemical Structure; Klein, D. J., Trinajstic, N., Eds.; Elsevier: New York, 1990; p 287.
65. (d) Cooper, D. L.; Gerratt, J.; Raimondi, M. In Advances in the Theory of Benzenoid Hydrocarbons; Gutman, I., Cyvin, S. J., Eds. Top. Curr. Chem. 1990, 153, 41.
66. For a recent review of the method, see: (a) Hiberty, P. C. In Modern Electronic Structure Theory and Applications in Organic Chemistry; Davidson, E. R., Ed.; World Scientific; River Edge, NJ, 1997; pp 289-367. (b) Hiberty, P. C. J. Mol. Struct. (THEOCHEM), 1998, 451, 237.
67. For a recent review of the method, see: (a) Hiberty, P. C. In Modern Electronic Structure Theory and Applications in Organic Chemistry; Davidson, E. R., Ed.; World Scientific; River Edge, NJ, 1997; pp 289-367. (b) Hiberty, P. C. J. Mol. Struct. (THEOCHEM), 1998, 451, 237.
68. The BOVB method was developed first in Hiberty, P. C.; Flament, J. P.; Noizet, E. Chem. Phys. Lett. 1992, 189, 259.
69. 8 are discussed in (a) Hiberty, P. C.; Humbel, S.; Byrman, C. P.; Van Lenthe, J. H. J. Chem. Phys. 1994, 101, 5969. (b) Hiberty, P. C.; Humbel, S.; Archirel, P. J. Phys. Chem. 1994, 98, 11697.
70. 8 are discussed in (a) Hiberty, P. C.; Humbel, S.; Byrman, C. P.; Van Lenthe, J. H. J. Chem. Phys. 1994, 101, 5969. (b) Hiberty, P. C.; Humbel, S.; Archirel, P. J. Phys. Chem. 1994, 98, 11697.
71. Chirgwin, H. B.; Coulson, C. A. Proc. R. Soc. London. Ser. A 1950, 2, 196.
72. (a) Weinhold, F.; Carpenter, J. E. In The Structure of Small Molecules and Ions; Naaman, R., Veger, Z., Eds.; Plenum: New York, 1988; p 227.
73. (b) Reed, A. E.; Curtiss, L. A.; Weinhold, F. Chem. Rev. 1988, 88, 899.
74. For findings of negative mixing coefficients in MO mixing, see: (a) Whangbo, M. H.; Hoffmann, R. J. Chem. Phys. 1978, 68, 5498. (b) Ammeter, J. H.; Bürgi, H.-B.; Thibeault, J. C.; Hoffmann, R. J. Am. Chem. Soc. 1978, 100, 3686.
75. For findings of negative mixing coefficients in MO mixing, see: (a) Whangbo, M. H.; Hoffmann, R. J. Chem. Phys. 1978, 68, 5498. (b) Ammeter, J. H.; Bürgi, H.-B.; Thibeault, J. C.; Hoffmann, R. J. Am. Chem. Soc. 1978, 100, 3686.
76. (a) Pauling's scale updated by Allred in 1961: Allred, A. L. J. Inorg. Nucl. Chem. 1961, 17, 215. (The first version of Pauling's scale: Pauling, L. J. Am. Chem. Soc. 1932, 54, 3570.)
77. (a) Pauling's scale updated by Allred in 1961: Allred, A. L. J. Inorg. Nucl. Chem. 1961, 17, 215. (The first version of Pauling's scale: Pauling, L. J. Am. Chem. Soc. 1932, 54, 3570.)
78. m = (I + A)/2): Mulliken, R. S. J. Chem. Phys. 1934, 2, 782.
79. (c) Allen, L. C. J. Am. Chem. Soc. 1989, 111, 9003
80. (d) Allred, A. L.; Rochow, E. G. J. Inorg. Nucl. Chem. 1958, 5, 264, 269.
81. Shaik, S.; Hiberty, P. C. Adv. Quantum Chem. 1995, 26, 99.
82. Strictly speaking, if the inactive orbitals of the various BOVB configurations are more different from what would be required by the mere breathing orbital effect that just adapts the shape of the orbitals to the charge fluctuation, part of the energy stabilization contributed by the mixing of the inverse ionic structure, but not all of it, could well be a bias due to correlation of the inactive pairs in the molecule but not in the fragments. It is not possible to quantify the precise magnitude of the bias, and in any event, it is clear that in the present situation it cannot be large.
83. Sanderson, R. T. Polar Covalence; Academic Press: New York, 1983.
84. (a) Lauvergnat, D.; Hiberty, P. C. J. Mol. Struct (THEOCHEM) 1995, 338, 283.
85. rep term contains the orbital relaxation effect of the fragments.
86. The BSI results are given at the SD-BOVB level whereas the BSII results refer to the D-BOVB level; however, preliminary examination showed that the split does not effect the shape of the curves (i.e., the minimum of the curves does not change due to splitting).
87. Frenking, G.; Fau, S.; Marchand, C. M.; Grützmacher, H. J. Am. Chem. Soc. 1997, 119, 6648.
88. Epiotis, N. D. Unified Valence Bond Theory of Electronic Structure. Applications. Lect. Notes Chem. 1983, 34, 265-285.
89. Shaik, S. In Encyclopedia of Computational Chemistry; Schleyer, P. v. R., Allinger, N. L., Clark, T., Gasteiger, J., Kollman, P. A., Schaefer, H. F., III, Eds.; John Wiley: Chichester, U.K., 1998; Vol. 5, pp 3143-3156.
90. 3C-Cl see: J. Phys. Chem. Ref. Data 1974, 3, 392.
91. 3Si-Cl see: J. Phys. Chem. Ref. Data 1982, 11, 745.
92. 3Ge-Cl see: Cradock, S.; McKean, D. C.; MacKlenzie, M. W. J. Mol. Struct. 1981, 74, 265.
93. 3Sn-Cl see: Bürger, H.; Betzel, M.; Schulz, P. J. Mol. Spectrosc. 1987, 121, 218.
94. (a) Curtiss, L. A.; Raghavachari, K.; Trucks, G. W.; Pople, J. A. J. Chem. Phys. 1991, 94, 7221.
95. (b) Pople, J. A.; Head-Gordon, M., Fox, D. J.; Raghavachari, K.; Curtiss, L. A. J. Chem. Phys. 1989, 90, 5622.
96. Lias, S. G.; Bartmess, J. E.; Liebman, J. F.; Holmes, J. L.; Levin, R. D.; Mallard, W. G. J. Phys. Chem. Ref. Data 1988, 17, Suppl. No. 1.
97. Walsh, R. Acc. Chem. Res. 1981, 14, 246.
98. Jackson, R. A. Special Publication No. 24, The Chemical Society, 1970, p 295. Taken from Free Radicals; Kochi, J. K., Ed.; Wiley and Sons: New York, Vol. 2, Chapter 25, p 743. Assuming that the influence of the R group which is attached to the M central atom on the strength of the M-Cl bond will be small and similar for all, one can see the same trend predicted by the calculations.
99. Jackson, R. A. Special Publication No. 24, The Chemical Society, 1970, p 295. Taken from Free Radicals; Kochi, J. K., Ed.; Wiley and Sons: New York, Vol. 2, Chapter 25, p 743. Assuming that the influence of the R group which is attached to the M central atom on the strength of the M-Cl bond will be small and similar for all, one can see the same trend predicted by the calculations.
100. Bickelhaupt, F. M.; Nibbering, N. M. M.; van Wezenbeeck, E. M.; Baerends, E. J. J. Phys. Chem. 1992, 96, 4864.
101. Kitaura, K.; Morokuma, K. Int. J. Quantum Chem. 1976, 10, 325.