Ab initio quantum chemistry calculations on the electronic structure of heavier alkyne congeners: Diradical character and reactivity

Journal of the American Chemical Society

Volumn 128, Issue 22, 2006, Pages 7185-7192

  Jung, Yousung ^a   Brynda, Marcin ^b   Power, Philip P ^b   Head Gordon, Martin ^a  

^a UNIVERSITY OF CALIFORNIA   (United States)

^b UNIVERSITY OF CALIFORNIA   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CHEMICAL ANALYSIS; CHEMICAL BONDS; HYDROCARBONS; MOLECULAR STRUCTURE; NUMERICAL ANALYSIS;

ALKYNE CONGENERS; GEOMETRIC DISTORTIONS; PLANAR TRANS BENT GEOMETRIES; QUANTUM CHEMISTRY;

ELECTRONIC STRUCTURE;

ALKYNE; GERMANIUM; LEAD; RADICAL; SILICON; TIN;

AB INITIO CALCULATION; ARTICLE; CHEMICAL BOND; CRYSTAL STRUCTURE; DENSITY FUNCTIONAL THEORY; GEOMETRY; QUANTUM CHEMISTRY; SOLID STATE; X RAY DIFFRACTION;

EID: 33744904186     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja055374c     Document Type: Article

References (58)

1. Pu, L.; Twamley, B.; Power, P. P. J. Am. Chem. Soc. 2000, 122, 3524.
2. Phillips, A. D.; Wright, R. J.; Olmstead, M. M.; Power, P. P. J. Am. Chem. Soc. 2002, 124, 5930.
3. Slender, M.; Phillips, A. D.; Wright, R. J.; Power, P. P. Angew. Chem., Int. Ed. 2002, 4l, 1785.
4. Wiberg, N.; Niedermayer, W.; Fischer, G.; Noth, H.; Suter, M. Eur. J. Inorg. Chem. 2002, 1066.
5. Sekiguchi, A.; Kinjo, R.; Ichinohe, M. Science (Washington, D.C.) 2004, 305, 1755.
6. Simons, R. S.; Power, P. P. J. Am. Chem. Soc. 1996, 118, 11966.
7. Su, J. R.; Li, X. W.; Crittendon, R. C.; Robinson, G. H. J. Am. Chem. Soc. 1997, 119, 5471.
8. Grutzmacher, H.; Fassler, T. F. Chem-Eur. J. 2000, 6, 2317.
9. Xie, J. M.; Grev, R. S.; Gu, J. D.; Schaefer, H. F.; Schleyer, P. v. R.; Su, J. R.; Li, X. W.; Robinson, G. H. J. Am. Chem. Soc. 1998, 120, 3773.
10. Xie, Y. M.; Schaefer, H. F.; Robinson, G. H. Chem. Phys. Lett. 2000, 317, 174.
11. Malcolm, N. O. J.; Gillespie, R. J.; Popelier, P. L. A. J. Chem. Soc., Dalton Trans. 2002, 3333.
12. Bridgeman, A. J.; Ireland, L. R. Polyhedron 2001, 20, 2841.
13. Grev, R. S. Adv. Organomet. Chem. 1991, 33, 125.
14. Chen, Y.; Hartmann, M.; Diedenhofen, M.; Frenking, G. Angew. Chem., Int. Ed. 2001, 40, 2052.
15. Pignedoli, C. A.; Curioni, A.; Andreoni, W. ChemPhysChem 2005, 6, 1795.
16. Allen, T. L.; Fink, W. H.; Power, P. P. J. Chem. Soc., Dalton Trans. 2000, 407.
17. Cui, C.; Brynda, M.; Olmstead, M. M.; Power, P. P. J. Am. Chem. Soc. 2004, 126, 6510.
18. Cui, C.; Olmstead, M. M.; Power, P. P. J. Am. Chem. Soc. 2004, 126, 5062.
19. Stender, M.; Phillips, A. D.; Power, P. P. Chem. Commun. (Cambridge) 2002, 1312.
20. Cui, C. M.; Olmstead, M. M.; Fettinger, J. C.; Spikes, G. H.; Power, P. P. J. Am. Chem. Soc. 2005, 127, 17530.
21. Yamaguchi, Y.; Deleeuw, B. J.; Richards, C. A.; Schaefer, H. F.; Frenking, G. J. Am. Chem. Soc. 1994, 116, 11922.
22. Snyder, L. C.; Wasserman, Z. R.; Moskowitz, J. W. Int. J. Quantum Chem. 1982, 21, 565.
23. Binkley, J. S. J. Am. Chem. Soc. 1984, 106, 603.
24. Lischka, H.; Koehler, H. J. J. Am. Chem. Soc. 1983, 105, 6646.
25. Luke, B. T.; Pople, J. A.; Krogh-Jespersen, M. B.; Apeloig, Y.; Karni, M.; Chandrasekhar, J.; Schleyer, P. v. R. J. Am. Chem. Soc. 1986, 108, 270.
26. Kobayashi, K.; Nagase, S. Organometallics 1997, 16, 2489.
27. Nagase, S.; Kobayashi, K.; Takagi, N. J. Organomet. Chem. 2000, 611, 264.
28. Sekiguchi, A.; Zigler, S. S.; West, R.; Michi, J. J. Am. Chem. Soc. 1986, 108, 4241.
29. Colegrove, B. T.; Schaefer, H. F., III. J. Phys. Chem. 1990, 94, 5593.
30. Colegrove, B. T.; Schaefer, H. F., III. J. Am. Chem. Soc. 1991, 113, 1557.
31. Koseki, S.; Gordon, M. S. J. Phys. Chem. 1988, 92, 364.
32. Kobayashi, K.; Takagi, N.; Nagase, S. Organometallics 2001, 20, 234.
33. Takagi, N.; Nagase, S. Chem. Lett. 2001, 966.
34. Takagi, N.; Nagase, S. Eur. J. Inorg. Chem. 2002, 2775.
35. Grev, R. S.; Deleeuw, B. J.; Schaefer, H. F., III. Chem. Phys. Lett. 1990, 165, 257.
36. Han, Y.-K.; Bac, C.; Lee, Y. S.; Lee, S. Y. J. Comput. Chem. 1998, 19, 1526.
37. Palagyi, Z.; Schaefer, H. F., III; Kapuy, E. J. Am. Chem. Soc. 1993, 115, 6901.
38. Lein, M.; Krapp, A.; Frenking, G. J. Am. Chem. Soc. 2005, 127, 6290.
39. Resonance forms of the heavier group 14 element alkyne molecules that feature a single electron at the group 14 atoms have been illustrated. See ref 11.
40. Nash, C. S.; Bursten, B. E.; Ermler, W. C. J. Chem. Phys. 1997, 106, 5133.
41. For a more flexible description of chemical bonding, we have added an uncontracted polarization d function for carbon (exponent = 0.80) and silicon (exponent = 0.284, see: Hollwarth, A.; et al. Chem. Phys. Lett. 1993, 208, 237-240) to the existing CRENEL basis, which we denoted as CRENBL*. For Sn and Pb, no extra polarization functions were added besides the original ones.
42. Kong, J.; et al. J. Comput. Chem. 2000, 21, 1532.
43. Shao, Y.; Head-Gordon, M.; Krylov, A. I. J. Chem. Phys. 2003, 118, 4807.
44. We note that a SiSi triple-bonded molecule synthesized by Sekiguchi and co-workers has a wider trans-bending angle (137.4°) and shorter SiSi distance (2.06 Å) than our model MeSiSiMe (128.4° and 2.14 Å), causing the compound to have stronger in-plane π overlap. This will make α for Sekiguchi's compound higher, as the author suggested it to be 0.62.
45. 2 is ∼60 kcal/mol.
46. Bonacickoutecky, V.; Koutecky, J.; Mictil, J. Angew. Chem., Int. Ed. Engl. 1987, 26, 170.
47. Dohnert, D.; Koutecky, J. J. Am. Chem. Soc. 1980, 102, 1789.
48. Flynn, C. R.; Michl, J. J. Am. Chem. Soc. 1974, 96, 3280.
49. Cullen, J. Chem. Phys. 1996, 202, 217.
50. Voorhis, T. V.; Head-Gordon, M. Chem. Phys. Lett. 2000, 317, 575.
51. Voorhis, T. V.; Head-Gordon, M. J. Chem. Phys. 2002, 117, 9190.
52. Jung, Y.; Head-Gordon, M. J. Phys. Chem. A 2003, 107, 7475.
53. Jung, Y.; Head-Gordon, M. ChemPhysChem 2003, 4, 522.
54. -.
55. out becomes lower in energy than LP* and occupied.
56. Takagi, N.; Nagase, S. Organometallics 2001, 20, 5498.
57. - Sn = 3.05 Å and Tbt-Sn-Sn = 97.3° is the global minimum and is more stable than the structure with Sn-Sn = 2.66 Å and Tbt-Sn-Sn = 122.0° by 2.4 kcal/mol (ref 56 and a private communication with the authors).
58. Pu, L.; Phillips, A. D.; Richards, A. F.; Slender, M.; Simons, R. S.; Olmstead, M. M.; Power, P. P. J. Am. Chem. Soc: 2003, 125, 11626.