Theoretical study of an isolable compound with a short silicon-silicon triple bond, (tBU3Si)2MeSiSi≡SiSiMe (SitBu3)2

European Journal of Inorganic Chemistry

Volumn , Issue 11, 2002, Pages 2775-2778

  Takagi, Nozomi ^a   Nagase, Shigeru ^a  

^a INSTITUTE FOR MOLECULAR SCIENCE   (Japan)

Author keywords

Density functional calculations; Multiple bonds; Silicon; Substituent effects

Indexed keywords

BOND LENGTH; SILICON; SILICON COMPOUNDS;

A-STABLE; DENSITY-FUNCTIONAL CALCULATIONS; DENSITY-FUNCTIONAL-THEORY; MULTIPLE BONDS; SI-SI BONDS; SILYL GROUP; SUBSTITUENT EFFECT; THEORETICAL STUDY; TRIPLE BONDS; WORKERS';

DENSITY FUNCTIONAL THEORY;

SILANE DERIVATIVE; SILICON;

ARTICLE; CALCULATION; CHEMICAL BOND; MOLECULAR STABILITY; QUANTUM CHEMISTRY; THEORY;

EID: 0036840239     PISSN: 14341948     EISSN: None     Source Type: Journal    
DOI: 10.1002/1099-0682(200211)2002:11<2775::AID-EJIC2775>3.0.CO;2-D     Document Type: Article

References (43)

1. R. West, M. J. Fink, J. Michl, Science 1981, 214, 1343-1344.
2. R. Okazaki, R. West, Adv. Organomet. Chem. 1996, 39, 231-273.
3. P. P. Power, Chem. Rev. 1999, 99, 3463-3503; P. P. Power, J. Chem. Soc., Dalton Trans. 1998, 2939-2951.
4. P. P. Power, Chem. Rev. 1999, 99, 3463-3503; P. P. Power, J. Chem. Soc., Dalton Trans. 1998, 2939-2951.
5. M. Weidenbruch, Eur. J. Inorg. Chem. 1999, 373-381; M. Weidenbruch, J. Organomet. Chem. 2002, 646, 39-52.
6. M. Weidenbruch, Eur. J. Inorg. Chem. 1999, 373-381; M. Weidenbruch, J. Organomet. Chem. 2002, 646, 39-52.
7. For a recent discussion on a Ga-Ga bond length as short as triple bonds, see: G. H. Robinson, Acc. Chem. Res. 1999, 32, 773-782; N. Takagi, M. W. Schmidt, S. Nagase, Organometallics 2001, 20, 1646-1651.
8. For a recent discussion on a Ga-Ga bond length as short as triple bonds, see: G. H. Robinson, Acc. Chem. Res. 1999, 32, 773-782; N. Takagi, M. W. Schmidt, S. Nagase, Organometallics 2001, 20, 1646-1651.
9. A. Sekiguchi, S. S. Zigler, R. West, J. Am. Chem. Soc. 1986, 108, 4241-4242.
10. R. Pietschnig, R. West, D. R. Powell, Organometallics 2000, 19, 2724-2729.
11. K. W. Klinkhammer. Angew. Chem. 1997, 109, 2414-2416; Angew. Chem. Int. Ed. Engl. 1997, 36, 2320-2322.
12. K. W. Klinkhammer. Angew. Chem. 1997, 109, 2414-2416; Angew. Chem. Int. Ed. Engl. 1997, 36, 2320-2322.
13. P. Jutzi, Angew. Chem. 2000, 112, 3953-3957; Angew. Chem. Int. Ed. 2000, 39, 3797-3800.
14. P. Jutzi, Angew. Chem. 2000, 112, 3953-3957; Angew. Chem. Int. Ed. 2000, 39, 3797-3800.
15. K. Kobayashi, S. Nagase, Organometallics 1997, 16, 2489-2491.
16. S. Nagase, K. Kobayashi, N. Takagi, J. Organomet. Chem. 2000, 611, 264-271.
17. K. Kobayashi, N. Takagi, S. Nagase, Organometallics 2001, 20, 234-236.
18. [13a] N. Takagi, S. Nagase, Chem. Lett. 2001, 966-967. It has recently been found that the structure with the central aryl rings of the terphenyl groups (Ar*) nearly coplanar to the Si≡Si part is 6.2 kcal/mol more stable than the somewhat more twisted structure (Si-Si = 2.126 Å, θ = 130.5 Å, and ω = 163.9°) with the central aryl rings perpendicular to Si≡Si.[13a] This trend has also been found for Ar*Ge≡GeAr* and Ar* Sn≡SnAr* (to be published).
19. N. Takagi, S. Nagase, Organometallics 2001, 20, 5498-5500.
20. For recent reviews on the stabilization and synthesis of doubly bonded compounds using the Tbt and Ar* groups, see: B. Twamley, S. T. Haubrich, P. P. Power, Adv. Organomet. Chem. 1999, 44, 1-65; J. A. C. Clyburne, N. McMullen, Coord. Chem. Res. 2000, 210, 73-99; R. Okazaki, N. Tokitoh, Acc. Chem. Res. 2000, 33, 625-630; T. Sasamori, Y. Arai, N. Takeda, R. Okazaki, Y. Fuyukawa, M. Kimura, S. Nagase, N. Tokitoh, Bull. Chem. Soc. Jpn. 2002, 75, 1-15.
21. For recent reviews on the stabilization and synthesis of doubly bonded compounds using the Tbt and Ar* groups, see: B. Twamley, S. T. Haubrich, P. P. Power, Adv. Organomet. Chem. 1999, 44, 1-65; J. A. C. Clyburne, N. McMullen, Coord. Chem. Res. 2000, 210, 73-99; R. Okazaki, N. Tokitoh, Acc. Chem. Res. 2000, 33, 625-630; T. Sasamori, Y. Arai, N. Takeda, R. Okazaki, Y. Fuyukawa, M. Kimura, S. Nagase, N. Tokitoh, Bull. Chem. Soc. Jpn. 2002, 75, 1-15.
22. For recent reviews on the stabilization and synthesis of doubly bonded compounds using the Tbt and Ar* groups, see: B. Twamley, S. T. Haubrich, P. P. Power, Adv. Organomet. Chem. 1999, 44, 1-65; J. A. C. Clyburne, N. McMullen, Coord. Chem. Res. 2000, 210, 73-99; R. Okazaki, N. Tokitoh, Acc. Chem. Res. 2000, 33, 625-630; T. Sasamori, Y. Arai, N. Takeda, R. Okazaki, Y. Fuyukawa, M. Kimura, S. Nagase, N. Tokitoh, Bull. Chem. Soc. Jpn. 2002, 75, 1-15.
23. For recent reviews on the stabilization and synthesis of doubly bonded compounds using the Tbt and Ar* groups, see: B. Twamley, S. T. Haubrich, P. P. Power, Adv. Organomet. Chem. 1999, 44, 1-65; J. A. C. Clyburne, N. McMullen, Coord. Chem. Res. 2000, 210, 73-99; R. Okazaki, N. Tokitoh, Acc. Chem. Res. 2000, 33, 625-630; T. Sasamori, Y. Arai, N. Takeda, R. Okazaki, Y. Fuyukawa, M. Kimura, S. Nagase, N. Tokitoh, Bull. Chem. Soc. Jpn. 2002, 75, 1-15.
24. For the synthesis and isolation of silabenzene, see: K. Wakita, N. Tokitoh, R. Okazaki, S. Nagase, Angew. Chem. 2000, 112, 648-650; Angew. Chem. Int. Ed. 2000, 39, 634-636; K. Wakita, N. Tokitoh, R. Okazaki, N. Takagi, S. Nagase, J. Am. Chem. Soc. 2000, 122, 5648-5649.
25. For the synthesis and isolation of silabenzene, see: K. Wakita, N. Tokitoh, R. Okazaki, S. Nagase, Angew. Chem. 2000, 112, 648-650; Angew. Chem. Int. Ed. 2000, 39, 634-636; K. Wakita, N. Tokitoh, R. Okazaki, N. Takagi, S. Nagase, J. Am. Chem. Soc. 2000, 122, 5648-5649.
26. For the synthesis and isolation of silabenzene, see: K. Wakita, N. Tokitoh, R. Okazaki, S. Nagase, Angew. Chem. 2000, 112, 648-650; Angew. Chem. Int. Ed. 2000, 39, 634-636; K. Wakita, N. Tokitoh, R. Okazaki, N. Takagi, S. Nagase, J. Am. Chem. Soc. 2000, 122, 5648-5649.
27. K. Kobayashi, S. Nagase, to be published.
28. N. Wiberg, W. Niedermayer, G. Fischer, H. Nöth, M. Suter, Eur. J. Inorg. Chem. 2002, 1066-1070.
29. A. D. Becke, Phys. Rev. 1988, A38, 3098-3100; A. D. Becke, J. Chem. Phys. 1993, 98, 5648-5652; C. Lee, W. Yang, R. G. Parr, Phys. Rev. 1988, B37, 785-789.
30. A. D. Becke, Phys. Rev. 1988, A38, 3098-3100; A. D. Becke, J. Chem. Phys. 1993, 98, 5648-5652; C. Lee, W. Yang, R. G. Parr, Phys. Rev. 1988, B37, 785-789.
31. A. D. Becke, Phys. Rev. 1988, A38, 3098-3100; A. D. Becke, J. Chem. Phys. 1993, 98, 5648-5652; C. Lee, W. Yang, R. G. Parr, Phys. Rev. 1988, B37, 785-789.
32. W. J. Pietro, M. M. Francl, W. J. Hehre, D. J. DeFrees, J. A. Pople, J. S. Binkley, J. Am. Chem. Soc. 1982, 104, 5039-5048.
33. M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, V. G. Zakrzewski, J. A. Montgomery Jr., R. E. Stratmann, J. C. Burant, S. Dapprich, J. M. Millam, A. D. Daniels, K. N. Kudin, M. C. Strain, O. Farkas, J. Tomasi, V. Barone, M. Cossi, R. Cammi, B. Mennucci, C. Pomelli, C. Adamo, S. Clifford, J. Ochterski, G. A. Petersson, P. Y. Ayala, Q. Cui, K. Morokuma, D. K. Malick, A. D. Rabuck, K. Raghavachari, J. B. Foresman, J. Cioslowski, J. V. Ortiz, B. B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. Gomperts, R. L. Martin, D. J. Fox, T. Keith, M. A. Al-Laham, C. Y. Peng, A. Nanayakkara, C. Gonzalez, M. Challacombe, P. M. W. Gill, B. Johnson, W. Chen, M W. Wong, J. L. Andres, M. Head-Gordon, E. S. Replogle, J. A. Pople, Gaussian 98, Gaussian, Inc., Pittsburgh, PA, 1998.
34. W. Kutzelnigg, Angew. Chem. 1984, 96, 262-286; Angew. Chem. Int. Ed. Engl. 1984, 23, 272-295.
35. W. Kutzelnigg, Angew. Chem. 1984, 96, 262-286; Angew. Chem. Int. Ed. Engl. 1984, 23, 272-295.
36. M. Kira, T. Maruyama, C. Kabuto, K. Ebata, H. Sakurai, Angew. Chem. 1994, 106, 1575-1577; Angew. Chem. Int. Ed. Engl. 1994, 33, 1489-1491.
37. M. Kira, T. Maruyama, C. Kabuto, K. Ebata, H. Sakurai, Angew. Chem. 1994, 106, 1575-1577; Angew. Chem. Int. Ed. Engl. 1994, 33, 1489-1491.
38. Upon the trans-bending, the low-lying vacant σ*-orbital is mixed into the in-plane π-orbital (a second-order Jahn-Teller effect); this orbital mixing contributes to stabilization but makes the π-bond slipped and weakened.
39. 2], see: N. Wiberg, W. Niedermayer, H. Nöth, M. Warchhold, Z. Anorg. Allg. Chem. 2001, 627, 1717-1722.
40. N. Wiberg, C. M. M. Finger, K. Polborn, Angew. Chem. 1993, 105, 1140-1142; Angew. Chem. Int. Ed. Engl. 1993, 32, 1054-1056; N. Wiberg, Coord. Chem. Rev. 1997, 163, 217-252.
41. N. Wiberg, C. M. M. Finger, K. Polborn, Angew. Chem. 1993, 105, 1140-1142; Angew. Chem. Int. Ed. Engl. 1993, 32, 1054-1056; N. Wiberg, Coord. Chem. Rev. 1997, 163, 217-252.
42. N. Wiberg, C. M. M. Finger, K. Polborn, Angew. Chem. 1993, 105, 1140-1142; Angew. Chem. Int. Ed. Engl. 1993, 32, 1054-1056; N. Wiberg, Coord. Chem. Rev. 1997, 163, 217-252.
43. 29Si NMR chemical shift at δ = 111.2 ppm calculated for R**Si≡SiR** is much closer to the observed signal than that at δ = 180.4 ppm calculated for R**ClSi=SiClR**.