CH3• is planar due to H-H steric repulsion. Theoretical study of MH3• and MH3Cl (M = C, Si, Ge, Sn)

Organometallics

Volumn 15, Issue 5, 1996, Pages 1477-1487

  Bickelhaupt, F Matthias ^a,b   Ziegler, Tom ^a   Von Ragué Schleyer, Paul ^a,c  

^a UNIVERSITY OF CALGARY   (Canada)

^b Department of Molecular Biology and Genetics   (United States)

^c UNIVERSITY OF ERLANGEN NUREMBERG   (Germany)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0001681968     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om950560k     Document Type: Article

References (111)

1. (a) March, J. Advanced Organic Chemistry; Wiley-Interscience: New York, 1992.
2. (b) Carey, F. A.; Sundberg, R. J. Advanced Organic Chemistry, Part A; Plenum Press: New York, 1984.
3. (c) Elschenbroich, Ch.; Salzer, A. Organometallics. A Concise Introduction, 2nd ed.; VCH: Weinheim, Germany, 1992.
4. (d) Collman, J. P.; Hegedus, L. S.; Norton, J. R.; Finke, R. G. Principles and Applications of Organotransition Metal Chemistry; University Science Books: Mill Valley, CA, 1987.
5. (a) Bürger, H.; Betzel, M.; Schultz, P. J. Mol. Spetrosc. 1987, 121, 218.
6. (b) Cradock, S.; McKean, D. C.; MacKenzie, M. W. J. Mol. Struct. 1981, 74, 265.
7. (c) Harmony, M. D.; Laurie, V. W.; Kuczkowski, R. L.; Schwendeman, R. H.; Ramsay, D. A.; Lovas, F. J.; Lafferty, W. J.; Maki, A. G. J. Phys. Chem. Ref. Data 1979, 8, 619.
8. (d) Callomon, J. H.; Hirota, E.; Kuchitsu, K.; Lafferty, W. J.; Maki, A. G.; Pote, C. S. In Strukturdaten freier mehratomiger Molekeln, Landolt-Börnstein, Neue Serie, Gruppe II: Atom- und Molekularphysik, Band 7; Hellwege, K.-H.; Hellwege, A. M., Eds.; Springer-Verlag: Berlin, 1976.
9. (a) 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.
10. (b) CRC Handbook of Chemistry and Physics, 63rd ed.; Weast, R. C., Ed.; CRC Press: Boca Raton, FL, 1982; p D-195.
11. (a) Sita, L. R. Acc. Chem. Res. 1994, 27, 191.
12. (b) Walsh, R. Acc. Chem. Res. 1981, 14, 246.
13. (a) Deng, L.; Branchadell, V.; Ziegler, T. J. Am. Chem. Soc. 1994, 116, 10645.
14. (b) Fujimoto, H.; Satoh, S. J. Phys. Chem. 1994, 98, 1436.
15. (c) Pearson, R. G. J. Am. Chem. Soc. 1985, 107, 6801.
16. (a) Schneider, W.; Thiel, W. Chem. Phys. 1992, 159, 49.
17. (b) Schneider, W.; Thiel, W. J. Chem. Phys. 1987, 86, 923.
18. (c) Shi, Z.; Boyd, R. J. J. Am. Chem. Soc. 1990, 112, 6789.
19. (d) Gordon, M. S.; Davis, L. P.; Burggraf, L. W. Chem. Phys. Lett. 1989, 163, 371.
20. (e) Schmidt, M. W.; Gordon, M. S. Can. J. Chem. 1985, 63, 1609.
21. (f) 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.
22. (g) Vacek, G.; Mastryukov, V. S.; Schaefer, H. F., III. J. Phys. Chem. 1994, 98, 11337.
23. (h) Berger, S.; Bock, W.; Frenking, G.; Jonas, V.; Müller, F. J. Am. Chem. Soc. 1995, 117, 3820.
24. (i) Su, M.-D.; Schlegel, H. B. J. Phys. Chem. 1993, 97, 8732.
25. (j) Coffey, D., Jr.; Smith, B. J.; Radom, L. J. Chem. Phys. 1993, 98, 3952.
26. (k) Binning, R. C., Jr.; Curtiss, L. A. J. Comput. Chem. 1990, 11, 1206.
27. (l) Ochterski, J. W.; Petersson, G. A.; Wiberg, K. B. J. Am. Chem. Soc. 1995, 117, 11299.
28. (m) Su, M.-D.; Schlegel, H. B. J. Phys. Chem. 1993, 97, 9981.
29. (a) Yamada, C.; Hirota, E.; Kawaguchi, K. J. Chem. Phys. 1981, 75, 5256.
30. (b) Yamada, C.; Hirota, E. Phys. Rev. Lett. 1986, 56, 923.
31. (c) Jackel, G. S.; Gordy, W. Phys. Rev. 1968, 176, 443.
32. (d) Jackel, G. S.; Christiansen, J. J.; Gordy, W. J. Chem. Phys. 1967, 47, 4274.
33. •; our corresponding NL-SCF/TZ2P values are 33, 31, 31, and 30%.
34. (f) Johnson, R. D., III; Tsai, B. P.; Hudgens, J. W. J. Chem. Phys. 1988, 89, 4558.
35. (a) Selmani, A.; Salahub, D. R. Chem. Phys. Lett. 1988, 146, 465.
36. (b) Moc, J.; Rudzinski, J. M.; Ratajczak, H. Chem. Phys. 1992, 109, 197.
37. (c) Chatgilialoglu, C.; Guerra, M. J. Am. Chem. Soc. 1990, 112, 2854.
38. (d) Trinquier, G. J. Chem. Soc., Faraday Trans. 1993, 89, 775.
39. (e) Michels, H. H.; Hobbs, R. H. Chem. Phys. Lett. 1993, 207, 389.
40. (f) Guerra, M. J. Am. Chem. Soc. 1993, 115, 11926.
41. (g) Moc, J.; Rudzinski, J. M.; Ratajczak, H. Z. Phys. D 1992, 22, 629.
42. (a) Cremer, D.; Olsson, L.; Ottosson, H. J. Mol. Struct. (THEOCHEM) 1994, 313, 91.
43. (b) Nyalászi, L.; Belghazi, A.; Szétsi, S. K.; Veszprémi, T.; Heinicke, J. J. Mol. Struct. (THEOCHEM) 1994, 313, 73.
44. (c) Rodriquez, C. F.; Hopkinson, A. C. Can. J. Chem. 1992, 70, 2234.
45. (d) Das, K. K.; Balasubramanian, K. J. Chem. Phys. 1990, 93, 5883.
46. (e) Green, W. H.; Jayatilaka, D.; Willetts, A.; Amos, R. D.; Handy, N. C. J. Chem. Phys. 1990, 93, 4965.
47. (f) Allen, W. D.; Schaefer, H. F., III. Chem. Phys. 1986, 108, 243.
48. (a) Binning, R. C., Jr.; Curtiss, L. A. J. Chem. Phys. 1990, 92, 3688.
49. (b) Binning, R. C., Jr.; Curtiss, L. A. J. Chem. Phys. 1990, 92, 1860.
50. (c) Pople, J. A.; Curtiss, L. A. J. Phys. Chem. 1987, 91, 155.
51. (d) Pople, J. A.; Luke, B. T.; Frisch, M. J.; Binkley, J. S. J. Phys. Chem. 1985, 89, 2198.
52. (e) Marynick, D. S. J. Chem. Phys. 1981, 74, 5186.
53. (a) Albright, T. A.; Burdett, J. K.; Whangbo, M.-H. Orbital Interactions in Chemistry; Wiley-Interscience: New York, 1985; Chapters 7 and 9.
54. (b) Gimarc, B. M. Molecular Structure and Bonding; Academic Press: New York, 1979; Chapter 3.
55. Gillespie, R. J.; Hargittai, I. The VSEPR Model of Molecular Geometry; Allyn and Bacon: Boston, MA, 1991.
56. Gilheany, D. G. Chem. Rev. 1994, 94, 1339.
57. (a) Dixon, D. A.; Arduengo, A. J., III. J. Am. Chem. Soc. 1987, 109, 338.
58. (b) Reed, A. E.; Schleyer, P. v. R. J. Am. Chem. Soc. 1987, 109, 7362.
59. (c) Magnusson, E. Tetrahedron 1985, 41, 5235.
60. (d) Ibid. 1985, 41, 2945.
61. (e) Magnusson, E. J. Am. Chem. Soc. 1984, 106, 1185.
62. (f) Magnusson, E. J. Am. Chem. Soc. 1984, 106, 1177.
63. (g) Hall, M. B. J. Am. Chem. Soc. 1978, 100, 6332.
64. Gobbi, A.; Frenking, G. J. Am. Chem. Soc. 1994, 116, 9287.
65. See for some examples the following references: (a) Gal, J.-F.; Grover, R.; Maria, P.-C.; Operti, L.; Rabezzana, R.; Vaglio, G.-A.; Volpe, P. J. Phys. Chem. 1994, 98, 11978. (b) Davies, P. B.; Smith, D. M. J. Chem. Phys. 1994, 100, 6166. (c) Lu, G.; Crowell, J. E. J. Chem. Phys. 1993, 98, 3415. (d) Operti, L.; Splendore, M.; Vaglio, G. A.; Volpe, P. Organometallics 1993, 12, 4516. (e) Schleyer, P. v. R.; Buzek, P.; Müller, T.; Apeloig, Y.; Siehl, H.-U. Angew. Chem. 1993, 105, 1558. (f) Ruscic, B.; Schwarz, M.; Berkowitz, J. J. Chem. Phys. 1990, 92, 1865. Erratum: Ibid. 1990, 92, 6338. (g) Raghavachari, K. J. Chem. Phys. 1990, 92, 452.
66. See for some examples the following references: (a) Gal, J.-F.; Grover, R.; Maria, P.-C.; Operti, L.; Rabezzana, R.; Vaglio, G.-A.; Volpe, P. J. Phys. Chem. 1994, 98, 11978. (b) Davies, P. B.; Smith, D. M. J. Chem. Phys. 1994, 100, 6166. (c) Lu, G.; Crowell, J. E. J. Chem. Phys. 1993, 98, 3415. (d) Operti, L.; Splendore, M.; Vaglio, G. A.; Volpe, P. Organometallics 1993, 12, 4516. (e) Schleyer, P. v. R.; Buzek, P.; Müller, T.; Apeloig, Y.; Siehl, H.-U. Angew. Chem. 1993, 105, 1558. (f) Ruscic, B.; Schwarz, M.; Berkowitz, J. J. Chem. Phys. 1990, 92, 1865. Erratum: Ibid. 1990, 92, 6338. (g) Raghavachari, K. J. Chem. Phys. 1990, 92, 452.
67. See for some examples the following references: (a) Gal, J.-F.; Grover, R.; Maria, P.-C.; Operti, L.; Rabezzana, R.; Vaglio, G.-A.; Volpe, P. J. Phys. Chem. 1994, 98, 11978. (b) Davies, P. B.; Smith, D. M. J. Chem. Phys. 1994, 100, 6166. (c) Lu, G.; Crowell, J. E. J. Chem. Phys. 1993, 98, 3415. (d) Operti, L.; Splendore, M.; Vaglio, G. A.; Volpe, P. Organometallics 1993, 12, 4516. (e) Schleyer, P. v. R.; Buzek, P.; Müller, T.; Apeloig, Y.; Siehl, H.-U. Angew. Chem. 1993, 105, 1558. (f) Ruscic, B.; Schwarz, M.; Berkowitz, J. J. Chem. Phys. 1990, 92, 1865. Erratum: Ibid. 1990, 92, 6338. (g) Raghavachari, K. J. Chem. Phys. 1990, 92, 452.
68. See for some examples the following references: (a) Gal, J.-F.; Grover, R.; Maria, P.-C.; Operti, L.; Rabezzana, R.; Vaglio, G.-A.; Volpe, P. J. Phys. Chem. 1994, 98, 11978. (b) Davies, P. B.; Smith, D. M. J. Chem. Phys. 1994, 100, 6166. (c) Lu, G.; Crowell, J. E. J. Chem. Phys. 1993, 98, 3415. (d) Operti, L.; Splendore, M.; Vaglio, G. A.; Volpe, P. Organometallics 1993, 12, 4516. (e) Schleyer, P. v. R.; Buzek, P.; Müller, T.; Apeloig, Y.; Siehl, H.-U. Angew. Chem. 1993, 105, 1558. (f) Ruscic, B.; Schwarz, M.; Berkowitz, J. J. Chem. Phys. 1990, 92, 1865. Erratum: Ibid. 1990, 92, 6338. (g) Raghavachari, K. J. Chem. Phys. 1990, 92, 452.
69. See for some examples the following references: (a) Gal, J.-F.; Grover, R.; Maria, P.-C.; Operti, L.; Rabezzana, R.; Vaglio, G.-A.; Volpe, P. J. Phys. Chem. 1994, 98, 11978. (b) Davies, P. B.; Smith, D. M. J. Chem. Phys. 1994, 100, 6166. (c) Lu, G.; Crowell, J. E. J. Chem. Phys. 1993, 98, 3415. (d) Operti, L.; Splendore, M.; Vaglio, G. A.; Volpe, P. Organometallics 1993, 12, 4516. (e) Schleyer, P. v. R.; Buzek, P.; Müller, T.; Apeloig, Y.; Siehl, H.-U. Angew. Chem. 1993, 105, 1558. (f) Ruscic, B.; Schwarz, M.; Berkowitz, J. J. Chem. Phys. 1990, 92, 1865. Erratum: Ibid. 1990, 92, 6338. (g) Raghavachari, K. J. Chem. Phys. 1990, 92, 452.
70. See for some examples the following references: (a) Gal, J.-F.; Grover, R.; Maria, P.-C.; Operti, L.; Rabezzana, R.; Vaglio, G.-A.; Volpe, P. J. Phys. Chem. 1994, 98, 11978. (b) Davies, P. B.; Smith, D. M. J. Chem. Phys. 1994, 100, 6166. (c) Lu, G.; Crowell, J. E. J. Chem. Phys. 1993, 98, 3415. (d) Operti, L.; Splendore, M.; Vaglio, G. A.; Volpe, P. Organometallics 1993, 12, 4516. (e) Schleyer, P. v. R.; Buzek, P.; Müller, T.; Apeloig, Y.; Siehl, H.-U. Angew. Chem. 1993, 105, 1558. (f) Ruscic, B.; Schwarz, M.; Berkowitz, J. J. Chem. Phys. 1990, 92, 1865. Erratum: Ibid. 1990, 92, 6338. (g) Raghavachari, K. J. Chem. Phys. 1990, 92, 452.
71. See for some examples the following references: (a) Gal, J.-F.; Grover, R.; Maria, P.-C.; Operti, L.; Rabezzana, R.; Vaglio, G.-A.; Volpe, P. J. Phys. Chem. 1994, 98, 11978. (b) Davies, P. B.; Smith, D. M. J. Chem. Phys. 1994, 100, 6166. (c) Lu, G.; Crowell, J. E. J. Chem. Phys. 1993, 98, 3415. (d) Operti, L.; Splendore, M.; Vaglio, G. A.; Volpe, P. Organometallics 1993, 12, 4516. (e) Schleyer, P. v. R.; Buzek, P.; Müller, T.; Apeloig, Y.; Siehl, H.-U. Angew. Chem. 1993, 105, 1558. (f) Ruscic, B.; Schwarz, M.; Berkowitz, J. J. Chem. Phys. 1990, 92, 1865. Erratum: Ibid. 1990, 92, 6338. (g) Raghavachari, K. J. Chem. Phys. 1990, 92, 452.
72. (a) Dreizler, R. M.; Gross, E. K. U. Density Functional Theory, An Approach to the Quantum Many-Body Problem; Springer-Verlag: Berlin, 1990.
73. (b) Parr, R. G.; Yang, W. Density-Functional Theory of Atoms and Molecules; Oxford University Press: New York, 1989.
74. (c) Slater, J. C. Quantum Theory of Molecules and Solids; McGraw-Hill: New York, 1974; Vol. 4.
75. (a) Ziegler, T. Chem. Rev. 1991, 91, 651.
76. (b) Density Functional Methods in Chemistry; Labanowski, J. K., Andzelm, J. W., Eds.; Springer-Verlag: New York, 1991.
77. (a) Baerends, E. J.; Ellis, D. E.; Ros, P. Chem. Phys. 1973, 2, 41.
78. (b) Baerends, E. J.; Ros, P. Chem. Phys. 1975, 8, 412.
79. (c) Baerends, E. J.; Ros, P. Int. J. Quantum Chem., Quantum Chem. Symp. 1978, S12, 169.
80. (d) Ravenek, W. In Algorithms and Applications on Vector and Parallel Computers; Riele, H. H. J., Dekker, Th. J., van de Vorst, H.A., Eds.; Elsevier: Amsterdam, 1987.
81. (e) Boerrigter, P. M.; te Velde, G.; Baerends, E. J. Int. J. Quantum Chem. 1988, 33, 87.
82. (f) te Velde, G.; Baerends, E. J. J. Comp. Phys. 1992, 99, 84.
83. (g) Snijders, J. G.; Baerends, E. J.; Vernooijs, P. At. Nucl. Data Tables 1982, 26, 483.
84. (h) Krijn, J.; Baerends, E. J. Fit-Functions in the HFS-Method, Internal Report (in Dutch), Vrije Universiteit Amsterdam, The Netherlands, 1984.
85. (i) Baker, J.; Nobes, R. H.; Radom, L. J. Comput. Chem. 1986, 7, 349.
86. (j) Gutsev, G. L.; Ziegler, T. J. Phys. Chem. 1991, 95, 7220.
87. (k) Gutsev, G. L.; Ziegler, T. Can. J. Chem. 1991, 69, 993.
88. (l) Versluis, L.; Ziegler, T. J. Chem. Phys. 1988, 88, 322.
89. (m) Fan, L.; Versluis, L.; Ziegler, T.; Baerends, E. J.; Ravenek, W. Int. J. Quantum Chem., Quantum Chem. Symp. 1988, S22, 173.
90. (n) Vosko, S. H.; Wilk, L.; Nusair, M. Can. J. Phys. 1980, 58, 1200.
91. (o) Becke, A. D. J. Chem. Phys. 1986, 84, 4524.
92. (p) Becke, A. D. Phys. Rev. A 1988, 38, 3098.
93. (q) Perdew, J. P. Phys. Rev. B 1986, 33, 8822. Erratum: Ibid. 1986, 34, 7406.
94. (r) Fan, L.; Ziegler, T. J. Chem. Phys. 1991, 94, 6057.
95. (a) Bickelhaupt, F. M.; Nibbering, N. M. M.; van Wezenbeek, E. M.; Baerends, E. J. J. Phys. Chem. 1992, 96, 4864.
96. (b) Ziegler, T.; Rauk, A. Inorg. Chem. 1979, 18, 1558.
97. (c) Ziegler, T.; Rauk, A. Inorg. Chem. 1979, 18, 1755.
98. (d) Ziegler, T.; Rauk, A. Theoret. Chim. Acta 1977, 46, 1.
99. (a) Jacobsen, H.; Ziegler, T. J. Am. Chem. Soc. 1994, 116, 3667.
100. (b) Kutzelnigg, W. Angew. Chem. 1984, 96, 262.
101. Bickelhaupt, F. M.; Ziegler, T.; Schleyer, P. v.R. Organometallics 1995, 14, 2288.
102. Rauk, A. Orbital Interaction Theory of Organic Chemistry; Wiley-Interscience: New York, 1994.
103. See also ref 11a, Chapter 5.2, and ref lib, Chapter 2.
104. In our approach, orbital energies occur naturally as a measure of (orbital) electronegativities of atoms or groups. Note that the trend in Pauling electronegativities for M, i.e., 2.55, 1.90, 2.01, and 1.96 for C, Si, Ge, and Sn, respectively, follows that of the AO energies and, in particular, that the irregular variation from Si via Ge to Sn correlates with the M-ns orbital energy (Figure 2). (b) Electronegativities were taken from: Boyd, R. J.; Markus, G. E. J. Chem. Phys. 1981, 75, 5385. (c) See also: Pauling, L. The Nature of the Chemical Bond; Cornell University Press: Ithaca, NY, 1960; Chapter 3.
105. In our approach, orbital energies occur naturally as a measure of (orbital) electronegativities of atoms or groups. Note that the trend in Pauling electronegativities for M, i.e., 2.55, 1.90, 2.01, and 1.96 for C, Si, Ge, and Sn, respectively, follows that of the AO energies and, in particular, that the irregular variation from Si via Ge to Sn correlates with the M-ns orbital energy (Figure 2). (b) Electronegativities were taken from: Boyd, R. J.; Markus, G. E. J. Chem. Phys. 1981, 75, 5385. (c) See also: Pauling, L. The Nature of the Chemical Bond; Cornell University Press: Ithaca, NY, 1960; Chapter 3.
106. Fleming, I. Grenzorbitale und-Reaktionen organischer Verbindungen; VCH Verlagsgesellschaft: Weinheim, Germany, 1990.
107. See, for example, the following studies and references cited therein: (a) Taketsugu, T.; Gordon, M. S. J. Phys. Chem. 1995, 99, 8462. (b) Windus, T. L.; Gordon, M. S.; Davis, L. P. Burggraf, L. W. J. Am. Chem. Soc. 1994, 116, 3568. (c) Ramsden, C. A. Chem. Soc. Rev. 1994, 111. (d) DePuy, C. H.; Damrauer, R.; Bowie, J. H.; Sheldon, J. C. Acc. Chem. Res. 1987, 20, 127.
108. See, for example, the following studies and references cited therein: (a) Taketsugu, T.; Gordon, M. S. J. Phys. Chem. 1995, 99, 8462. (b) Windus, T. L.; Gordon, M. S.; Davis, L. P. Burggraf, L. W. J. Am. Chem. Soc. 1994, 116, 3568. (c) Ramsden, C. A. Chem. Soc. Rev. 1994, 111. (d) DePuy, C. H.; Damrauer, R.; Bowie, J. H.; Sheldon, J. C. Acc. Chem. Res. 1987, 20, 127.
109. See, for example, the following studies and references cited therein: (a) Taketsugu, T.; Gordon, M. S. J. Phys. Chem. 1995, 99, 8462. (b) Windus, T. L.; Gordon, M. S.; Davis, L. P. Burggraf, L. W. J. Am. Chem. Soc. 1994, 116, 3568. (c) Ramsden, C. A. Chem. Soc. Rev. 1994, 111. (d) DePuy, C. H.; Damrauer, R.; Bowie, J. H.; Sheldon, J. C. Acc. Chem. Res. 1987, 20, 127.
110. See, for example, the following studies and references cited therein: (a) Taketsugu, T.; Gordon, M. S. J. Phys. Chem. 1995, 99, 8462. (b) Windus, T. L.; Gordon, M. S.; Davis, L. P. Burggraf, L. W. J. Am. Chem. Soc. 1994, 116, 3568. (c) Ramsden, C. A. Chem. Soc. Rev. 1994, 111. (d) DePuy, C. H.; Damrauer, R.; Bowie, J. H.; Sheldon, J. C. Acc. Chem. Res. 1987, 20, 127.
111. Bickelhaupt, F. M.; Ziegler, T.; Schleyer, P. v.R. To be published.