First Structural Characterization of a Benzophenone Ketyl Complex

Angewandte Chemie (International Edition in English)

Volumn 36, Issue 12, 1997, Pages 1292-1294

  Hou, Zhaomin ^a   Jia, Xueshun ^a   Hoshino, Mikio ^a   Wakatsuki, Yasuo ^a  

^a INST OF PHYS AND CHEMICAL RESEARCH   (Japan)

Author keywords

Arenes; Calcium; Radicals; Reductions; Structure elucidation

Indexed keywords

EID: 0030848345     PISSN: 05700833     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.199712921     Document Type: Article

References (38)

1. For early examples of the formation of ketyl species, see a) F. Bechman, T. Paul, Justus Ann. Client. 1891, 266, 1; b) W. Schlenk, T. Weichel, Ber. Dtsch. Chem. Ges. 1911, 44, 1182; c) W. Schlenk, A. Thai, ibid. 1913, 46, 2840.
2. For early examples of the formation of ketyl species, see a) F. Bechman, T. Paul, Justus Ann. Client. 1891, 266, 1; b) W. Schlenk, T. Weichel, Ber. Dtsch. Chem. Ges. 1911, 44, 1182; c) W. Schlenk, A. Thai, ibid. 1913, 46, 2840.
3. For early examples of the formation of ketyl species, see a) F. Bechman, T. Paul, Justus Ann. Client. 1891, 266, 1; b) W. Schlenk, T. Weichel, Ber. Dtsch. Chem. Ges. 1911, 44, 1182; c) W. Schlenk, A. Thai, ibid. 1913, 46, 2840.
4. For reviews on metal ketyl mediated organic synthesis, see a) A. Fürstner, B. Bogdanovic, Angew. Chem. 1996, 108, 2582; Angew. Chem. Int. Ed. Engl. 1996, 35, 2442; b) T. Wirth, ibid. 1996, 35, 61 and 1996, 108, 65; c) J. W. Huffman in Comprehensive Organic Synthesis, Vol. 8 (Eds.: B. M. Trost, I. Fleming), Pergamon, Oxford, 1991, p. 104; d) G. M. Robertson in Comprehensive Organic Synthesis, Vol. 3 (Eds. B. M. Trost, I. Fleming, G. Pattenden), Pergamon, Oxford, 1991, p. 563; e) J. E. McMurry, Chem. Rev. 1989, 89, 1513; f) B. E. Kahn, R. T. Riecke, ibid. 1988, 88, 733; g) S. K. Pradhan, Tetrahedron 1986, 42, 6351; h) J. W. Huffman, Acc. Chem. Res. 1983, 16, 399; i) J. E. McMurry, ibid. 1983, 16, 405; ibid. 1974, 7, 281; j) H. O. House, Modern Synthetic Reactions, 2nd ed., W. A. Benjamin, Menlo Park, CA, 1972, p. 145.
5. For reviews on metal ketyl mediated organic synthesis, see a) A. Fürstner, B. Bogdanovic, Angew. Chem. 1996, 108, 2582; Angew. Chem. Int. Ed. Engl. 1996, 35, 2442; b) T. Wirth, ibid. 1996, 35, 61 and 1996, 108, 65; c) J. W. Huffman in Comprehensive Organic Synthesis, Vol. 8 (Eds.: B. M. Trost, I. Fleming), Pergamon, Oxford, 1991, p. 104; d) G. M. Robertson in Comprehensive Organic Synthesis, Vol. 3 (Eds. B. M. Trost, I. Fleming, G. Pattenden), Pergamon, Oxford, 1991, p. 563; e) J. E. McMurry, Chem. Rev. 1989, 89, 1513; f) B. E. Kahn, R. T. Riecke, ibid. 1988, 88, 733; g) S. K. Pradhan, Tetrahedron 1986, 42, 6351; h) J. W. Huffman, Acc. Chem. Res. 1983, 16, 399; i) J. E. McMurry, ibid. 1983, 16, 405; ibid. 1974, 7, 281; j) H. O. House, Modern Synthetic Reactions, 2nd ed., W. A. Benjamin, Menlo Park, CA, 1972, p. 145.
6. For reviews on metal ketyl mediated organic synthesis, see a) A. Fürstner, B. Bogdanovic, Angew. Chem. 1996, 108, 2582; Angew. Chem. Int. Ed. Engl. 1996, 35, 2442; b) T. Wirth, ibid. 1996, 35, 61 and 1996, 108, 65; c) J. W. Huffman in Comprehensive Organic Synthesis, Vol. 8 (Eds.: B. M. Trost, I. Fleming), Pergamon, Oxford, 1991, p. 104; d) G. M. Robertson in Comprehensive Organic Synthesis, Vol. 3 (Eds. B. M. Trost, I. Fleming, G. Pattenden), Pergamon, Oxford, 1991, p. 563; e) J. E. McMurry, Chem. Rev. 1989, 89, 1513; f) B. E. Kahn, R. T. Riecke, ibid. 1988, 88, 733; g) S. K. Pradhan, Tetrahedron 1986, 42, 6351; h) J. W. Huffman, Acc. Chem. Res. 1983, 16, 399; i) J. E. McMurry, ibid. 1983, 16, 405; ibid. 1974, 7, 281; j) H. O. House, Modern Synthetic Reactions, 2nd ed., W. A. Benjamin, Menlo Park, CA, 1972, p. 145.
7. For reviews on metal ketyl mediated organic synthesis, see a) A. Fürstner, B. Bogdanovic, Angew. Chem. 1996, 108, 2582; Angew. Chem. Int. Ed. Engl. 1996, 35, 2442; b) T. Wirth, ibid. 1996, 35, 61 and 1996, 108, 65; c) J. W. Huffman in Comprehensive Organic Synthesis, Vol. 8 (Eds.: B. M. Trost, I. Fleming), Pergamon, Oxford, 1991, p. 104; d) G. M. Robertson in Comprehensive Organic Synthesis, Vol. 3 (Eds. B. M. Trost, I. Fleming, G. Pattenden), Pergamon, Oxford, 1991, p. 563; e) J. E. McMurry, Chem. Rev. 1989, 89, 1513; f) B. E. Kahn, R. T. Riecke, ibid. 1988, 88, 733; g) S. K. Pradhan, Tetrahedron 1986, 42, 6351; h) J. W. Huffman, Acc. Chem. Res. 1983, 16, 399; i) J. E. McMurry, ibid. 1983, 16, 405; ibid. 1974, 7, 281; j) H. O. House, Modern Synthetic Reactions, 2nd ed., W. A. Benjamin, Menlo Park, CA, 1972, p. 145.
8. For reviews on metal ketyl mediated organic synthesis, see a) A. Fürstner, B. Bogdanovic, Angew. Chem. 1996, 108, 2582; Angew. Chem. Int. Ed. Engl. 1996, 35, 2442; b) T. Wirth, ibid. 1996, 35, 61 and 1996, 108, 65; c) J. W. Huffman in Comprehensive Organic Synthesis, Vol. 8 (Eds.: B. M. Trost, I. Fleming), Pergamon, Oxford, 1991, p. 104; d) G. M. Robertson in Comprehensive Organic Synthesis, Vol. 3 (Eds. B. M. Trost, I. Fleming, G. Pattenden), Pergamon, Oxford, 1991, p. 563; e) J. E. McMurry, Chem. Rev. 1989, 89, 1513; f) B. E. Kahn, R. T. Riecke, ibid. 1988, 88, 733; g) S. K. Pradhan, Tetrahedron 1986, 42, 6351; h) J. W. Huffman, Acc. Chem. Res. 1983, 16, 399; i) J. E. McMurry, ibid. 1983, 16, 405; ibid. 1974, 7, 281; j) H. O. House, Modern Synthetic Reactions, 2nd ed., W. A. Benjamin, Menlo Park, CA, 1972, p. 145.
9. For reviews on metal ketyl mediated organic synthesis, see a) A. Fürstner, B. Bogdanovic, Angew. Chem. 1996, 108, 2582; Angew. Chem. Int. Ed. Engl. 1996, 35, 2442; b) T. Wirth, ibid. 1996, 35, 61 and 1996, 108, 65; c) J. W. Huffman in Comprehensive Organic Synthesis, Vol. 8 (Eds.: B. M. Trost, I. Fleming), Pergamon, Oxford, 1991, p. 104; d) G. M. Robertson in Comprehensive Organic Synthesis, Vol. 3 (Eds. B. M. Trost, I. Fleming, G. Pattenden), Pergamon, Oxford, 1991, p. 563; e) J. E. McMurry, Chem. Rev. 1989, 89, 1513; f) B. E. Kahn, R. T. Riecke, ibid. 1988, 88, 733; g) S. K. Pradhan, Tetrahedron 1986, 42, 6351; h) J. W. Huffman, Acc. Chem. Res. 1983, 16, 399; i) J. E. McMurry, ibid. 1983, 16, 405; ibid. 1974, 7, 281; j) H. O. House, Modern Synthetic Reactions, 2nd ed., W. A. Benjamin, Menlo Park, CA, 1972, p. 145.
10. For reviews on metal ketyl mediated organic synthesis, see a) A. Fürstner, B. Bogdanovic, Angew. Chem. 1996, 108, 2582; Angew. Chem. Int. Ed. Engl. 1996, 35, 2442; b) T. Wirth, ibid. 1996, 35, 61 and 1996, 108, 65; c) J. W. Huffman in Comprehensive Organic Synthesis, Vol. 8 (Eds.: B. M. Trost, I. Fleming), Pergamon, Oxford, 1991, p. 104; d) G. M. Robertson in Comprehensive Organic Synthesis, Vol. 3 (Eds. B. M. Trost, I. Fleming, G. Pattenden), Pergamon, Oxford, 1991, p. 563; e) J. E. McMurry, Chem. Rev. 1989, 89, 1513; f) B. E. Kahn, R. T. Riecke, ibid. 1988, 88, 733; g) S. K. Pradhan, Tetrahedron 1986, 42, 6351; h) J. W. Huffman, Acc. Chem. Res. 1983, 16, 399; i) J. E. McMurry, ibid. 1983, 16, 405; ibid. 1974, 7, 281; j) H. O. House, Modern Synthetic Reactions, 2nd ed., W. A. Benjamin, Menlo Park, CA, 1972, p. 145.
11. For reviews on metal ketyl mediated organic synthesis, see a) A. Fürstner, B. Bogdanovic, Angew. Chem. 1996, 108, 2582; Angew. Chem. Int. Ed. Engl. 1996, 35, 2442; b) T. Wirth, ibid. 1996, 35, 61 and 1996, 108, 65; c) J. W. Huffman in Comprehensive Organic Synthesis, Vol. 8 (Eds.: B. M. Trost, I. Fleming), Pergamon, Oxford, 1991, p. 104; d) G. M. Robertson in Comprehensive Organic Synthesis, Vol. 3 (Eds. B. M. Trost, I. Fleming, G. Pattenden), Pergamon, Oxford, 1991, p. 563; e) J. E. McMurry, Chem. Rev. 1989, 89, 1513; f) B. E. Kahn, R. T. Riecke, ibid. 1988, 88, 733; g) S. K. Pradhan, Tetrahedron 1986, 42, 6351; h) J. W. Huffman, Acc. Chem. Res. 1983, 16, 399; i) J. E. McMurry, ibid. 1983, 16, 405; ibid. 1974, 7, 281; j) H. O. House, Modern Synthetic Reactions, 2nd ed., W. A. Benjamin, Menlo Park, CA, 1972, p. 145.
12. For reviews on metal ketyl mediated organic synthesis, see a) A. Fürstner, B. Bogdanovic, Angew. Chem. 1996, 108, 2582; Angew. Chem. Int. Ed. Engl. 1996, 35, 2442; b) T. Wirth, ibid. 1996, 35, 61 and 1996, 108, 65; c) J. W. Huffman in Comprehensive Organic Synthesis, Vol. 8 (Eds.: B. M. Trost, I. Fleming), Pergamon, Oxford, 1991, p. 104; d) G. M. Robertson in Comprehensive Organic Synthesis, Vol. 3 (Eds. B. M. Trost, I. Fleming, G. Pattenden), Pergamon, Oxford, 1991, p. 563; e) J. E. McMurry, Chem. Rev. 1989, 89, 1513; f) B. E. Kahn, R. T. Riecke, ibid. 1988, 88, 733; g) S. K. Pradhan, Tetrahedron 1986, 42, 6351; h) J. W. Huffman, Acc. Chem. Res. 1983, 16, 399; i) J. E. McMurry, ibid. 1983, 16, 405; ibid. 1974, 7, 281; j) H. O. House, Modern Synthetic Reactions, 2nd ed., W. A. Benjamin, Menlo Park, CA, 1972, p. 145.
13. For reviews on metal ketyl mediated organic synthesis, see a) A. Fürstner, B. Bogdanovic, Angew. Chem. 1996, 108, 2582; Angew. Chem. Int. Ed. Engl. 1996, 35, 2442; b) T. Wirth, ibid. 1996, 35, 61 and 1996, 108, 65; c) J. W. Huffman in Comprehensive Organic Synthesis, Vol. 8 (Eds.: B. M. Trost, I. Fleming), Pergamon, Oxford, 1991, p. 104; d) G. M. Robertson in Comprehensive Organic Synthesis, Vol. 3 (Eds. B. M. Trost, I. Fleming, G. Pattenden), Pergamon, Oxford, 1991, p. 563; e) J. E. McMurry, Chem. Rev. 1989, 89, 1513; f) B. E. Kahn, R. T. Riecke, ibid. 1988, 88, 733; g) S. K. Pradhan, Tetrahedron 1986, 42, 6351; h) J. W. Huffman, Acc. Chem. Res. 1983, 16, 399; i) J. E. McMurry, ibid. 1983, 16, 405; ibid. 1974, 7, 281; j) H. O. House, Modern Synthetic Reactions, 2nd ed., W. A. Benjamin, Menlo Park, CA, 1972, p. 145.
14. For reviews on metal ketyl mediated organic synthesis, see a) A. Fürstner, B. Bogdanovic, Angew. Chem. 1996, 108, 2582; Angew. Chem. Int. Ed. Engl. 1996, 35, 2442; b) T. Wirth, ibid. 1996, 35, 61 and 1996, 108, 65; c) J. W. Huffman in Comprehensive Organic Synthesis, Vol. 8 (Eds.: B. M. Trost, I. Fleming), Pergamon, Oxford, 1991, p. 104; d) G. M. Robertson in Comprehensive Organic Synthesis, Vol. 3 (Eds. B. M. Trost, I. Fleming, G. Pattenden), Pergamon, Oxford, 1991, p. 563; e) J. E. McMurry, Chem. Rev. 1989, 89, 1513; f) B. E. Kahn, R. T. Riecke, ibid. 1988, 88, 733; g) S. K. Pradhan, Tetrahedron 1986, 42, 6351; h) J. W. Huffman, Acc. Chem. Res. 1983, 16, 399; i) J. E. McMurry, ibid. 1983, 16, 405; ibid. 1974, 7, 281; j) H. O. House, Modern Synthetic Reactions, 2nd ed., W. A. Benjamin, Menlo Park, CA, 1972, p. 145.
15. For reviews on metal ketyl mediated organic synthesis, see a) A. Fürstner, B. Bogdanovic, Angew. Chem. 1996, 108, 2582; Angew. Chem. Int. Ed. Engl. 1996, 35, 2442; b) T. Wirth, ibid. 1996, 35, 61 and 1996, 108, 65; c) J. W. Huffman in Comprehensive Organic Synthesis, Vol. 8 (Eds.: B. M. Trost, I. Fleming), Pergamon, Oxford, 1991, p. 104; d) G. M. Robertson in Comprehensive Organic Synthesis, Vol. 3 (Eds. B. M. Trost, I. Fleming, G. Pattenden), Pergamon, Oxford, 1991, p. 563; e) J. E. McMurry, Chem. Rev. 1989, 89, 1513; f) B. E. Kahn, R. T. Riecke, ibid. 1988, 88, 733; g) S. K. Pradhan, Tetrahedron 1986, 42, 6351; h) J. W. Huffman, Acc. Chem. Res. 1983, 16, 399; i) J. E. McMurry, ibid. 1983, 16, 405; ibid. 1974, 7, 281; j) H. O. House, Modern Synthetic Reactions, 2nd ed., W. A. Benjamin, Menlo Park, CA, 1972, p. 145.
16. For reviews on metal ketyl mediated organic synthesis, see a) A. Fürstner, B. Bogdanovic, Angew. Chem. 1996, 108, 2582; Angew. Chem. Int. Ed. Engl. 1996, 35, 2442; b) T. Wirth, ibid. 1996, 35, 61 and 1996, 108, 65; c) J. W. Huffman in Comprehensive Organic Synthesis, Vol. 8 (Eds.: B. M. Trost, I. Fleming), Pergamon, Oxford, 1991, p. 104; d) G. M. Robertson in Comprehensive Organic Synthesis, Vol. 3 (Eds. B. M. Trost, I. Fleming, G. Pattenden), Pergamon, Oxford, 1991, p. 563; e) J. E. McMurry, Chem. Rev. 1989, 89, 1513; f) B. E. Kahn, R. T. Riecke, ibid. 1988, 88, 733; g) S. K. Pradhan, Tetrahedron 1986, 42, 6351; h) J. W. Huffman, Acc. Chem. Res. 1983, 16, 399; i) J. E. McMurry, ibid. 1983, 16, 405; ibid. 1974, 7, 281; j) H. O. House, Modern Synthetic Reactions, 2nd ed., W. A. Benjamin, Menlo Park, CA, 1972, p. 145.
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22. For example, sodium benzophenone ketyl has been used by almost every chemist in the dehydration and deoxygenation of etheral solvents.
23. For examples of spectroscopic studies on benzophenone ketyl species, see a) P. H. Rieger, G. K. Fraenkel, J. Chem. Phys. 1962, 37, 2811; b) P. B. Ayscough, R. Wilson, J. Chem. Soc. 1963, 5412; c) N. Hirota, S. I. Weissman, J. Am. Chem. Soc. 1964, 86, 2538; d) N. Hirota, ibid. 1967, 89, 32; e) R. Dams, M. Malinowski, I. Westdorp, H. Y. Geise, J. Org. Chem. 1982, 47, 248; f) K. J. Covert, P. T. Wolczanski, S. A. Hill, P. J. Krusic, Inorg. Chem. 1992, 31, 66.
24. For examples of spectroscopic studies on benzophenone ketyl species, see a) P. H. Rieger, G. K. Fraenkel, J. Chem. Phys. 1962, 37, 2811; b) P. B. Ayscough, R. Wilson, J. Chem. Soc. 1963, 5412; c) N. Hirota, S. I. Weissman, J. Am. Chem. Soc. 1964, 86, 2538; d) N. Hirota, ibid. 1967, 89, 32; e) R. Dams, M. Malinowski, I. Westdorp, H. Y. Geise, J. Org. Chem. 1982, 47, 248; f) K. J. Covert, P. T. Wolczanski, S. A. Hill, P. J. Krusic, Inorg. Chem. 1992, 31, 66.
25. For examples of spectroscopic studies on benzophenone ketyl species, see a) P. H. Rieger, G. K. Fraenkel, J. Chem. Phys. 1962, 37, 2811; b) P. B. Ayscough, R. Wilson, J. Chem. Soc. 1963, 5412; c) N. Hirota, S. I. Weissman, J. Am. Chem. Soc. 1964, 86, 2538; d) N. Hirota, ibid. 1967, 89, 32; e) R. Dams, M. Malinowski, I. Westdorp, H. Y. Geise, J. Org. Chem. 1982, 47, 248; f) K. J. Covert, P. T. Wolczanski, S. A. Hill, P. J. Krusic, Inorg. Chem. 1992, 31, 66.
26. For examples of spectroscopic studies on benzophenone ketyl species, see a) P. H. Rieger, G. K. Fraenkel, J. Chem. Phys. 1962, 37, 2811; b) P. B. Ayscough, R. Wilson, J. Chem. Soc. 1963, 5412; c) N. Hirota, S. I. Weissman, J. Am. Chem. Soc. 1964, 86, 2538; d) N. Hirota, ibid. 1967, 89, 32; e) R. Dams, M. Malinowski, I. Westdorp, H. Y. Geise, J. Org. Chem. 1982, 47, 248; f) K. J. Covert, P. T. Wolczanski, S. A. Hill, P. J. Krusic, Inorg. Chem. 1992, 31, 66.
27. For examples of spectroscopic studies on benzophenone ketyl species, see a) P. H. Rieger, G. K. Fraenkel, J. Chem. Phys. 1962, 37, 2811; b) P. B. Ayscough, R. Wilson, J. Chem. Soc. 1963, 5412; c) N. Hirota, S. I. Weissman, J. Am. Chem. Soc. 1964, 86, 2538; d) N. Hirota, ibid. 1967, 89, 32; e) R. Dams, M. Malinowski, I. Westdorp, H. Y. Geise, J. Org. Chem. 1982, 47, 248; f) K. J. Covert, P. T. Wolczanski, S. A. Hill, P. J. Krusic, Inorg. Chem. 1992, 31, 66.
28. For examples of spectroscopic studies on benzophenone ketyl species, see a) P. H. Rieger, G. K. Fraenkel, J. Chem. Phys. 1962, 37, 2811; b) P. B. Ayscough, R. Wilson, J. Chem. Soc. 1963, 5412; c) N. Hirota, S. I. Weissman, J. Am. Chem. Soc. 1964, 86, 2538; d) N. Hirota, ibid. 1967, 89, 32; e) R. Dams, M. Malinowski, I. Westdorp, H. Y. Geise, J. Org. Chem. 1982, 47, 248; f) K. J. Covert, P. T. Wolczanski, S. A. Hill, P. J. Krusic, Inorg. Chem. 1992, 31, 66.
29. R. S. P. Coutts, P. C. Wailes, R. L. Martin, J. Organomet. Chem. 1971, 50, 145.
30. J. Takats, J. Alloys Compmls, in press.
31. Only the structures of sodium and samarium ketyl complexes have been reported [3].
32. For examples of spectroscopic studies on alkaline earth metal ketyl species, see a) S. W. Mao, N. Hirota, Chem. Phys. Lett. 1973, 22, 26; b) S. W. Mao, K. Nakamura, N. Hirota, J. Am. Chem. Soc. 1974, 96, 5341; see also ref. [5c].
33. For examples of spectroscopic studies on alkaline earth metal ketyl species, see a) S. W. Mao, N. Hirota, Chem. Phys. Lett. 1973, 22, 26; b) S. W. Mao, K. Nakamura, N. Hirota, J. Am. Chem. Soc. 1974, 96, 5341; see also ref. [5c].
34. 2. Crystallographic data (excluding structure factors) for the structures reported in this paper have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication no. CCDC-100217. Copies of the data can be obtained free of charge on application to The Director, CCDC, 12 Union Road, Cambridge CB21EZ, UK (fax: int. code +(1223)336-033; e-mail: deposit@chemcrys.cam.ac.uk).
35. P. B. Hitchcock, M. F. Lappert, G. A. Lawless, B. Royo, J. Chem. Soc. Chem. Commun. 1990, 1141.
36. The similarity in length between M-O(fluorenone ketyl) bonds and M-OAr bonds was previously observed; see ref. [3].
37. E. B. Fleischer, N. Sung, S. Hawkinson, J. Phys. Chem. 1968, 72, 4311.
38. Abstraction of a hydrogen atom from an alcohol by a fluorenone ketyl was previously observed; see ref. [3d].