Chemistry of borabenzene: Efficient and general synthesis of new neutral borabenzene-ligand complexes

Organometallics

Volumn 15, Issue 4, 1996, Pages 1315-1318

  Hoic, Diego A ^a   Wolf, Jennifer Robbins ^a   Davis, William M ^a   Fu, Gregory C ^a  

^a MASSACHUSETTS INSTITUTE OF TECHNOLOGY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000638713     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om9505569     Document Type: Article

References (29)

1. (a) Herberich, G. E.; Greiss, G.; Heil, H. F. Angew. Chem., Int. Ed. Engl. 1970, 9, 805-806.
2. (b) Ashe, A. J.; Shu, P. J. Am. Chem. Soc. 1971, 93, 1804-1805.
3. For leading references, see: (a) Herberich, G. E.; Ohst, H. Adv. Organomet. Chem. 1986, 25, 199-236. (b) Herberich, G. E.; Schmidt, B.; Englert, U. Organometallics 1995, 14, 471-480.
4. For leading references, see: (a) Herberich, G. E.; Ohst, H. Adv. Organomet. Chem. 1986, 25, 199-236. (b) Herberich, G. E.; Schmidt, B.; Englert, U. Organometallics 1995, 14, 471-480.
5. (a) Borabenzene-pyridine: Boese, R.; Finke, N.; Henkelmann, J.; Maier, G.; Paetzold, P.; Reisenauer, H. P.; Schmid, G. Chem. Ber, 1985, 118, 1644-1654. See also: Boese, R.; Finke, N.; Keil, T.; Paetzold, P.; Schmid, G. Z. Naturforsch., B 1985, 40, 1327-1332.
6. (a) Borabenzene-pyridine: Boese, R.; Finke, N.; Henkelmann, J.; Maier, G.; Paetzold, P.; Reisenauer, H. P.; Schmid, G. Chem. Ber, 1985, 118, 1644-1654. See also: Boese, R.; Finke, N.; Keil, T.; Paetzold, P.; Schmid, G. Z. Naturforsch., B 1985, 40, 1327-1332.
7. 2: Maier, G.; Reisenauer, H. P.; Henkelmann, J.; Kliche, C. Angew. Chem., Int. Ed. Engl. 1988, 27, 295-296.
8. (a) Pyridine- and triethylamine-2-boranaphthalene: Reference 3a. (b) (Dimethyl sulfide)-9-boraanthracene: Jutzi, P. Angew. Chem., Int. Ed. Engl. 1971, 10, 838.
9. For computational studies of free borabenzene and of neutral borabenzene-ligand complexes, see: (a) Schulman, J. M.; Disch, R. L.; Sabio, M. I. J. Am. Chem. Soc. 1982, 104, 3785-3788. (b) Raabe, G.; Heyne, E.; Schleker, W.; Fleischhauer, J. Z. Naturforsch., A 1984, 39, 678-681. (c) Raabe, G.; Schleker, W.; Heyne, E.; Fleischhauer, J. Z. Naturforsch., A 1987, 42, 352-360. (d) Schulman, J. M.; Disch, R. L. Organometallics 1989, 8, 733-737. (e) Cioslowski, J.; Hay, P. J. J. Am. Chem. Soc. 1990, 112, 1707-1710.
10. For computational studies of free borabenzene and of neutral borabenzene-ligand complexes, see: (a) Schulman, J. M.; Disch, R. L.; Sabio, M. I. J. Am. Chem. Soc. 1982, 104, 3785-3788. (b) Raabe, G.; Heyne, E.; Schleker, W.; Fleischhauer, J. Z. Naturforsch., A 1984, 39, 678-681. (c) Raabe, G.; Schleker, W.; Heyne, E.; Fleischhauer, J. Z. Naturforsch., A 1987, 42, 352-360. (d) Schulman, J. M.; Disch, R. L. Organometallics 1989, 8, 733-737. (e) Cioslowski, J.; Hay, P. J. J. Am. Chem. Soc. 1990, 112, 1707-1710.
11. For computational studies of free borabenzene and of neutral borabenzene-ligand complexes, see: (a) Schulman, J. M.; Disch, R. L.; Sabio, M. I. J. Am. Chem. Soc. 1982, 104, 3785-3788. (b) Raabe, G.; Heyne, E.; Schleker, W.; Fleischhauer, J. Z. Naturforsch., A 1984, 39, 678-681. (c) Raabe, G.; Schleker, W.; Heyne, E.; Fleischhauer, J. Z. Naturforsch., A 1987, 42, 352-360. (d) Schulman, J. M.; Disch, R. L. Organometallics 1989, 8, 733-737. (e) Cioslowski, J.; Hay, P. J. J. Am. Chem. Soc. 1990, 112, 1707-1710.
12. For computational studies of free borabenzene and of neutral borabenzene-ligand complexes, see: (a) Schulman, J. M.; Disch, R. L.; Sabio, M. I. J. Am. Chem. Soc. 1982, 104, 3785-3788. (b) Raabe, G.; Heyne, E.; Schleker, W.; Fleischhauer, J. Z. Naturforsch., A 1984, 39, 678-681. (c) Raabe, G.; Schleker, W.; Heyne, E.; Fleischhauer, J. Z. Naturforsch., A 1987, 42, 352-360. (d) Schulman, J. M.; Disch, R. L. Organometallics 1989, 8, 733-737. (e) Cioslowski, J.; Hay, P. J. J. Am. Chem. Soc. 1990, 112, 1707-1710.
13. For computational studies of free borabenzene and of neutral borabenzene-ligand complexes, see: (a) Schulman, J. M.; Disch, R. L.; Sabio, M. I. J. Am. Chem. Soc. 1982, 104, 3785-3788. (b) Raabe, G.; Heyne, E.; Schleker, W.; Fleischhauer, J. Z. Naturforsch., A 1984, 39, 678-681. (c) Raabe, G.; Schleker, W.; Heyne, E.; Fleischhauer, J. Z. Naturforsch., A 1987, 42, 352-360. (d) Schulman, J. M.; Disch, R. L. Organometallics 1989, 8, 733-737. (e) Cioslowski, J.; Hay, P. J. J. Am. Chem. Soc. 1990, 112, 1707-1710.
14. 1,4-Pentadiyne is not commercially available. For preparations of this difficult-to-isolate compound, see: (a) Ben-Efraim, D. A.; Sondheimer, F. Tetrahedron 1969, 25, 2823-2835. (b) Verkruijsse, H. D.; Hasselaar, M. Synthesis 1979, 292-293.
15. 1,4-Pentadiyne is not commercially available. For preparations of this difficult-to-isolate compound, see: (a) Ben-Efraim, D. A.; Sondheimer, F. Tetrahedron 1969, 25, 2823-2835. (b) Verkruijsse, H. D.; Hasselaar, M. Synthesis 1979, 292-293.
16. Ashe, A, J., III; Chan, W.-T.; Smith, T. W.; Taba, K. M. J. Org. Chem. 1981, 46, 881-885.
17. 3 produces the more reactive bromine analogue of 7; preliminary results indicate that this compound also serves as a precursor to neutral borabenzene-ligand adducts.
18. 3a
19. However, we were not able to generate the borabenzene-(2,6-di-tert-butyl-4-methylpyridine) complex by this route. Amendola, M. C. Unpublished results.
20. Using this procedure, we have synthesized, but not yet fully characterized, a number of other neutral borabenzene-ligand complexes (e.g., phosphite and arsine adducts).
21. The thermail, photochemical, and base-induced isomerization of related compounds has been reported: (a) Maier, G.; Henkelmann, J.; Reisenauer, H. P. Angew. Chem., Int. Ed. Engl. 1985, 24, 1065-1066. (b) Maier, G. Pure Appl. Chem. 1986, 58, 95-104.
22. The thermail, photochemical, and base-induced isomerization of related compounds has been reported: (a) Maier, G.; Henkelmann, J.; Reisenauer, H. P. Angew. Chem., Int. Ed. Engl. 1985, 24, 1065-1066. (b) Maier, G. Pure Appl. Chem. 1986, 58, 95-104.
23. Covalent radii: boron, 0.82 Å; carbon, 0.77 A. Gordon, A. J.; Ford, R. A. The Chemist's Companion; Wiley: New York, 1972; pp 82-83.
24. 3: X = Cl, 1.957-(5) Å; X = Br, 1.924(12) Å; X = I, 1.918(15) Å. Black, D. L.; Taylor, R. C. Acta Crystallogr., Sect. B 1975, 31, 1116-1120.
25. Hoic, D. A.; Davis, W. M.; Fu, G. C. J. Am. Chem. Soc. 1995, 117, 8480-8481.
26. Ashe, A. J., III; Chan, W.-T.; Smith, T. W.; Taba, K. M. J. Org. Chem. 1981, 46, 881-885. These workers effect the same cyclization under somewhat different conditions (refluxing heptane, 16 h) and observe a 34% yield of stannacycle 6.
27. 2 in the presence of metallic tin or other adventitious impurities (Kuivila, H. G. Adv. Organomet. Chem. 1964, 1, 47-87). We recommend that dibutyltin dihydride be prepared (Hayashi, K.; Iyoda, J.; Shiihara, I. J. Organomet. Chem. 1967, 10, 81-94) immediately prior to use.
28. 2 in the presence of metallic tin or other adventitious impurities (Kuivila, H. G. Adv. Organomet. Chem. 1964, 1, 47-87). We recommend that dibutyltin dihydride be prepared (Hayashi, K.; Iyoda, J.; Shiihara, I. J. Organomet. Chem. 1967, 10, 81-94) immediately prior to use.
29. If the product is not distilled quickly, some isomerization to boracycle 8 is observed.