Triple bonds to silicon. Substituent effects on the thermodynamic and kinetic stabilities of silynes relative to their isomeric silylidenes and silavinylidenes

Organometallics

Volumn 16, Issue 3, 1997, Pages 310-312

  Apeloig, Yitzhak ^a   Karni, Miriam ^a  

^a TECHNION ISRAEL INSTITUTE OF TECHNOLOGY   (Israel)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000339369     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om960844k     Document Type: Article

References (50)

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3. (c) Okazaki, R.; West, R. Adv. Organomet. Chem. 1996, 39, 231.
4. (d) For synthetic studies on Si=N, Si=P, Si=As, and Si=S the reader is referred to: (i) Hesse, M.; Klingebiel, U. Angew. Chem., Int. Ed. Engl. 1986, 25, 649. (ii) Driess, M. Angew. Chem., Int. Ed. Engl. 1991, 30, 1022. Bender, H. R. G.; Niecke, E.; Nieger, M. J. Am. Chem. Soc. 1993, 115, 3314. (iii) Driess, M.; Pritzkow, H. Angew. Chem., Int. Ed. Engl. 1992, 31, 816. (iv) Suzuki, H.; Tokitoh, N.; Nagase, S.; Okazaki, R. J. Am. Chem. Soc. 1994, 116, 11578.
5. (d) For synthetic studies on Si=N, Si=P, Si=As, and Si=S the reader is referred to: (i) Hesse, M.; Klingebiel, U. Angew. Chem., Int. Ed. Engl. 1986, 25, 649. (ii) Driess, M. Angew. Chem., Int. Ed. Engl. 1991, 30, 1022. Bender, H. R. G.; Niecke, E.; Nieger, M. J. Am. Chem. Soc. 1993, 115, 3314. (iii) Driess, M.; Pritzkow, H. Angew. Chem., Int. Ed. Engl. 1992, 31, 816. (iv) Suzuki, H.; Tokitoh, N.; Nagase, S.; Okazaki, R. J. Am. Chem. Soc. 1994, 116, 11578.
6. (d) For synthetic studies on Si=N, Si=P, Si=As, and Si=S the reader is referred to: (i) Hesse, M.; Klingebiel, U. Angew. Chem., Int. Ed. Engl. 1986, 25, 649. (ii) Driess, M. Angew. Chem., Int. Ed. Engl. 1991, 30, 1022. Bender, H. R. G.; Niecke, E.; Nieger, M. J. Am. Chem. Soc. 1993, 115, 3314. (iii) Driess, M.; Pritzkow, H. Angew. Chem., Int. Ed. Engl. 1992, 31, 816. (iv) Suzuki, H.; Tokitoh, N.; Nagase, S.; Okazaki, R. J. Am. Chem. Soc. 1994, 116, 11578.
7. (d) For synthetic studies on Si=N, Si=P, Si=As, and Si=S the reader is referred to: (i) Hesse, M.; Klingebiel, U. Angew. Chem., Int. Ed. Engl. 1986, 25, 649. (ii) Driess, M. Angew. Chem., Int. Ed. Engl. 1991, 30, 1022. Bender, H. R. G.; Niecke, E.; Nieger, M. J. Am. Chem. Soc. 1993, 115, 3314. (iii) Driess, M.; Pritzkow, H. Angew. Chem., Int. Ed. Engl. 1992, 31, 816. (iv) Suzuki, H.; Tokitoh, N.; Nagase, S.; Okazaki, R. J. Am. Chem. Soc. 1994, 116, 11578.
8. (d) For synthetic studies on Si=N, Si=P, Si=As, and Si=S the reader is referred to: (i) Hesse, M.; Klingebiel, U. Angew. Chem., Int. Ed. Engl. 1986, 25, 649. (ii) Driess, M. Angew. Chem., Int. Ed. Engl. 1991, 30, 1022. Bender, H. R. G.; Niecke, E.; Nieger, M. J. Am. Chem. Soc. 1993, 115, 3314. (iii) Driess, M.; Pritzkow, H. Angew. Chem., Int. Ed. Engl. 1992, 31, 816. (iv) Suzuki, H.; Tokitoh, N.; Nagase, S.; Okazaki, R. J. Am. Chem. Soc. 1994, 116, 11578.
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11. 3f
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19. Koseki, S.; Gordon, M. S. J. Phys. Chem. 1988, 92, 364. Koseki, S.; Gordon, M. S. J. Phys. Chem. 1989, 93, 118. Colgrove, B. T.; Schaefer, H. F., III. J. Phys. Chem. 1990, 94, 5593. Grev, R.; Schaefer, H. F., III. J. Chem. Phys. 1992, 97, 7990.
20. Koseki, S.; Gordon, M. S. J. Phys. Chem. 1988, 92, 364. Koseki, S.; Gordon, M. S. J. Phys. Chem. 1989, 93, 118. Colgrove, B. T.; Schaefer, H. F., III. J. Phys. Chem. 1990, 94, 5593. Grev, R.; Schaefer, H. F., III. J. Chem. Phys. 1992, 97, 7990.
21. Koseki, S.; Gordon, M. S. J. Phys. Chem. 1988, 92, 364. Koseki, S.; Gordon, M. S. J. Phys. Chem. 1989, 93, 118. Colgrove, B. T.; Schaefer, H. F., III. J. Phys. Chem. 1990, 94, 5593. Grev, R.; Schaefer, H. F., III. J. Chem. Phys. 1992, 97, 7990.
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34. The calculations were carried out using the Gaussian 92 package of programs. Gaussian 92: Frisch, M. J.; Trucks, G. W.; Head-Gordon, M.; Gill, P. M. W.; Wong, M. W.; Foresman, J. B.; Johnson, B. G.; Schlegel, H. B.; Robb, M. A.; Replogle, E. S.; Goperts, R.; Andres, J. L.; Raghavachari, K.; Binkley, J. S.; Gonzalez, C.; Martin, R. L.; Fox, D. J.; Defrees, D. J.; Baker, J.; Stewart, J. J. P.; Pople, J. A. GAUSSIAN 92/DFT, Revision G; Gaussian Inc.: Pittsburgh, 1992.
35. 2 at HF/6-31G*//3-21G, see ref 7b.
36. The best experimental-theoretical agreement is obtained using the MP2/6-31G(2df,p) optimized geometries. However as the relative energies of 2-4 (R = H) are hardly affected by increasing the basis set, we assume that MP4SDTQ/6-31G(d,p)//MP2/6-31G(d,p) calculations can be used for estimating reliably the relative energies of the various stationary points on the RHSiC PES.
37. Relative energies in the text are given at the MP4SDTQ/6-31G**//MP2/6-31G** + ZPE level unless otherwise stated.
38. For all systems the effect of entropy on the relative energies of the isomers is very small, and ΔG is therefore very similar to the relative energies given in Figure 1.
39. Walsh, R. In ref 1a, pp 371-391.
40. Ochterski. J. W.; Peterson, G. A.; Wiberg, K. B. J. Am. Chem. Soc. 1995, 117, 11299.
41. (a) H-rearrangements converting RSi≡CH to HRSi=C: have very high barriers (ca. 50 kcal/mol), and therefore they are not viable disappearance channels for the silynes (Figure 1).
42. (b) FHSi=C: and (HO)HSi=C: are predicted to rearrange rapidly to FSi≡CH and HOSi≡CH, respectively (Figure 1).
43. 10 that the correct Si≡C bond length is 1.65-1.66 Å, a value which is intermediate between our MP2 and QCISD values.
44. (a) Weinhold, F. NBO 4.0 Program Manual, 1996.
45. Glendening, E. D.; Weinhold, F. J. Comput. Chem. 1996, submitted for publication.
46. (b) Wiberg, K. B. Tetrahedron 1968, 24, 1083. Mayer, I. Chem. Phys. Lett. 1983, 97, 270.
47. (b) Wiberg, K. B. Tetrahedron 1968, 24, 1083. Mayer, I. Chem. Phys. Lett. 1983, 97, 270.
48. (c) The covalent and ionic (in parentheses) contributions to the NRT bond orders of 2b, R = H, F, and OH, are 2.31 (0.62), 2.06 (0.74), and 2.05 (0.71), respectively. The Wiberg bond orders correspond only to the covalent contribution to the NRT bond orders.
49. For R = R′ = Ph, Δ is relatively high (18.9 kcal/mol) because the phenyl rings in 3 can rotate to minimize their steric interactions. However, bulky ortho-substituents may change this situation.
50. Tokitoh, N.; Suzuki, H.; Okazaki, R.; Ogawa, K. J. Am. Chem. Soc. 1993, 115, 10428.