Synthesis, structure, spectroscopy, and reactivity of a neutral iridathiabenzene

Organometallics

Volumn 23, Issue 17, 2004, Pages 4139-4149

  Bleeke, John R ^a   Hinkle, Paul V ^a   Shokeen, Monica ^a   Rath, Nigam P ^b  

^a WASHINGTON UNIVERSITY   (United States)

^b UNIVERSITY OF MISSOURI ST LOUIS   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

AROMATIC RING SYSTEMS; ELECTROPHILES; METALLOAROMATICITY; NUCLEOPHILES;

ISOMERS; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; PARAMETER ESTIMATION; PROBABILITY; REACTION KINETICS; RESONANCE; SOLUTIONS; SULFUR; SYNTHESIS (CHEMICAL); THERMAL EFFECTS; X RAY CRYSTALLOGRAPHY; X RAY DIFFRACTION;

ORGANOMETALLICS;

EID: 4344605879     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om0400649     Document Type: Article

References (41)

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2. Metallacyclohexadiene and Metallabenzene Chemistry. 18. Part 17: Bleeke, J. R.; Hinkle, P. V.; Rath, N. P. Organometallics 2001, 20, 1939. See also: Bleeke, J. R.; Hinkle, P. V. J. Am. Chem. Soc. 1999, 121, 595.
3. Metallacyclohexadiene and Metallabenzene Chemistry. 18. Part 17: Bleeke, J. R.; Hinkle, P. V.; Rath, N. P. Organometallics 2001, 20, 1939. See also: Bleeke, J. R.; Hinkle, P. V. J. Am. Chem. Soc. 1999, 121, 595.
4. Bleeke, J. R.; Behm, R.; Xie, Y.-F.; Chiang, M. Y.; Robinson, K. D.; Beatty, A. M. Organometallics 1097, 16, 606. For a recent review of metallabenzenes, see: Bleeke, J. R. Chem. Rev. 2001, 101, 1205.
5. Bleeke, J. R.; Behm, R.; Xie, Y.-F.; Chiang, M. Y.; Robinson, K. D.; Beatty, A. M. Organometallics 1097, 16, 606. For a recent review of metallabenzenes, see: Bleeke, J. R. Chem. Rev. 2001, 101, 1205.
6. (a) Bleeke, J. R.; Blanchard, J. M. B.; Donnay, E. Organometallics 2001, 20, 324.
7. (b) Bleeke, J. R.; Blanchard, J. M. B. J. Am. Chem. Soc. 1997, 119, 5443.
8. Several other examples of metallathiabenzenes have been reported: (a) Chen, J.; Daniels, L. M.; Angelici, R. J. J. Am. Chem. Soc. 1990, 112, 199. (b) Chen, J.; Daniels, L. M.; Angelici, R. J. Polyhedron 1990, 9, 1883. (c) Chin, R. M.; Jones, W. D. Angew. Chem., Int. Ed. Engl. 1992, 31, 357. (d) Jones, W. D.; Chin, R. M. J. Am. Chem. Soc. 1992, 114, 9851. (e) Bianchini, C.; Meli, A.; Peruzzini, M.; Vizza, F.; Frediani, P.; Herrera, V.; Sanchez-Delgado, R. A. J. Am. Chem. Soc. 1993, 115, 2731. (f) Bianchini, C.; Meli, A.; Peruzzini, M.; Vizza, F.; Moneti, S.; Herrera, V.; Sanchez-Delgado, R. J. Am. Chem. Soc. 1994, 116, 4370.
9. Several other examples of metallathiabenzenes have been reported: (a) Chen, J.; Daniels, L. M.; Angelici, R. J. J. Am. Chem. Soc. 1990, 112, 199. (b) Chen, J.; Daniels, L. M.; Angelici, R. J. Polyhedron 1990, 9, 1883. (c) Chin, R. M.; Jones, W. D. Angew. Chem., Int. Ed. Engl. 1992, 31, 357. (d) Jones, W. D.; Chin, R. M. J. Am. Chem. Soc. 1992, 114, 9851. (e) Bianchini, C.; Meli, A.; Peruzzini, M.; Vizza, F.; Frediani, P.; Herrera, V.; Sanchez-Delgado, R. A. J. Am. Chem. Soc. 1993, 115, 2731. (f) Bianchini, C.; Meli, A.; Peruzzini, M.; Vizza, F.; Moneti, S.; Herrera, V.; Sanchez-Delgado, R. J. Am. Chem. Soc. 1994, 116, 4370.
10. Several other examples of metallathiabenzenes have been reported: (a) Chen, J.; Daniels, L. M.; Angelici, R. J. J. Am. Chem. Soc. 1990, 112, 199. (b) Chen, J.; Daniels, L. M.; Angelici, R. J. Polyhedron 1990, 9, 1883. (c) Chin, R. M.; Jones, W. D. Angew. Chem., Int. Ed. Engl. 1992, 31, 357. (d) Jones, W. D.; Chin, R. M. J. Am. Chem. Soc. 1992, 114, 9851. (e) Bianchini, C.; Meli, A.; Peruzzini, M.; Vizza, F.; Frediani, P.; Herrera, V.; Sanchez-Delgado, R. A. J. Am. Chem. Soc. 1993, 115, 2731. (f) Bianchini, C.; Meli, A.; Peruzzini, M.; Vizza, F.; Moneti, S.; Herrera, V.; Sanchez-Delgado, R. J. Am. Chem. Soc. 1994, 116, 4370.
11. Several other examples of metallathiabenzenes have been reported: (a) Chen, J.; Daniels, L. M.; Angelici, R. J. J. Am. Chem. Soc. 1990, 112, 199. (b) Chen, J.; Daniels, L. M.; Angelici, R. J. Polyhedron 1990, 9, 1883. (c) Chin, R. M.; Jones, W. D. Angew. Chem., Int. Ed. Engl. 1992, 31, 357. (d) Jones, W. D.; Chin, R. M. J. Am. Chem. Soc. 1992, 114, 9851. (e) Bianchini, C.; Meli, A.; Peruzzini, M.; Vizza, F.; Frediani, P.; Herrera, V.; Sanchez-Delgado, R. A. J. Am. Chem. Soc. 1993, 115, 2731. (f) Bianchini, C.; Meli, A.; Peruzzini, M.; Vizza, F.; Moneti, S.; Herrera, V.; Sanchez-Delgado, R. J. Am. Chem. Soc. 1994, 116, 4370.
12. Several other examples of metallathiabenzenes have been reported: (a) Chen, J.; Daniels, L. M.; Angelici, R. J. J. Am. Chem. Soc. 1990, 112, 199. (b) Chen, J.; Daniels, L. M.; Angelici, R. J. Polyhedron 1990, 9, 1883. (c) Chin, R. M.; Jones, W. D. Angew. Chem., Int. Ed. Engl. 1992, 31, 357. (d) Jones, W. D.; Chin, R. M. J. Am. Chem. Soc. 1992, 114, 9851. (e) Bianchini, C.; Meli, A.; Peruzzini, M.; Vizza, F.; Frediani, P.; Herrera, V.; Sanchez-Delgado, R. A. J. Am. Chem. Soc. 1993, 115, 2731. (f) Bianchini, C.; Meli, A.; Peruzzini, M.; Vizza, F.; Moneti, S.; Herrera, V.; Sanchez-Delgado, R. J. Am. Chem. Soc. 1994, 116, 4370.
13. Several other examples of metallathiabenzenes have been reported: (a) Chen, J.; Daniels, L. M.; Angelici, R. J. J. Am. Chem. Soc. 1990, 112, 199. (b) Chen, J.; Daniels, L. M.; Angelici, R. J. Polyhedron 1990, 9, 1883. (c) Chin, R. M.; Jones, W. D. Angew. Chem., Int. Ed. Engl. 1992, 31, 357. (d) Jones, W. D.; Chin, R. M. J. Am. Chem. Soc. 1992, 114, 9851. (e) Bianchini, C.; Meli, A.; Peruzzini, M.; Vizza, F.; Frediani, P.; Herrera, V.; Sanchez-Delgado, R. A. J. Am. Chem. Soc. 1993, 115, 2731. (f) Bianchini, C.; Meli, A.; Peruzzini, M.; Vizza, F.; Moneti, S.; Herrera, V.; Sanchez-Delgado, R. J. Am. Chem. Soc. 1994, 116, 4370.
14. Several platinacycles (references a-c) and nickelacycles (references d, e) that are closely related to the metallathiabenzenes cited in ref 4 have been reported. However, spectroscopic and structural data suggest that these molecules are better described as metallathiacy-clohexa-1,3-dienes. See: (a) Garcia, J. J.; Mann, B. E.; Adams, H.; Bailey, N. A.; Maitlis, P. M. J. Am. Chem. Soc. 1995, 117, 2179. (b) Garcia, J. J.; Arevalo, A.; Capella, S.; Chehata, A.; Hernandez, M.; Montiel, V.; Picazo, G.; Del Rio, F.; Toscano, R. A.; Adams, H.; Maitlis, P. M. Polyhedron 1997, 16, 3185. (c) Arevalo, A.; Bernes, S.; Garcia, J. J.; Maitlis, P. M. Organometallics 1999, 18, 1680. (d) Vicic, D. A.; Jones, W. D. J. Am. Chem. Soc. 1997, 119, 10855. (e) Vicic, D. A.; Jones, W. D. J. Am. Chem. Soc. 1999, 121, 7606.
15. Several platinacycles (references a-c) and nickelacycles (references d, e) that are closely related to the metallathiabenzenes cited in ref 4 have been reported. However, spectroscopic and structural data suggest that these molecules are better described as metallathiacy-clohexa-1,3-dienes. See: (a) Garcia, J. J.; Mann, B. E.; Adams, H.; Bailey, N. A.; Maitlis, P. M. J. Am. Chem. Soc. 1995, 117, 2179. (b) Garcia, J. J.; Arevalo, A.; Capella, S.; Chehata, A.; Hernandez, M.; Montiel, V.; Picazo, G.; Del Rio, F.; Toscano, R. A.; Adams, H.; Maitlis, P. M. Polyhedron 1997, 16, 3185. (c) Arevalo, A.; Bernes, S.; Garcia, J. J.; Maitlis, P. M. Organometallics 1999, 18, 1680. (d) Vicic, D. A.; Jones, W. D. J. Am. Chem. Soc. 1997, 119, 10855. (e) Vicic, D. A.; Jones, W. D. J. Am. Chem. Soc. 1999, 121, 7606.
16. Several platinacycles (references a-c) and nickelacycles (references d, e) that are closely related to the metallathiabenzenes cited in ref 4 have been reported. However, spectroscopic and structural data suggest that these molecules are better described as metallathiacy-clohexa-1,3-dienes. See: (a) Garcia, J. J.; Mann, B. E.; Adams, H.; Bailey, N. A.; Maitlis, P. M. J. Am. Chem. Soc. 1995, 117, 2179. (b) Garcia, J. J.; Arevalo, A.; Capella, S.; Chehata, A.; Hernandez, M.; Montiel, V.; Picazo, G.; Del Rio, F.; Toscano, R. A.; Adams, H.; Maitlis, P. M. Polyhedron 1997, 16, 3185. (c) Arevalo, A.; Bernes, S.; Garcia, J. J.; Maitlis, P. M. Organometallics 1999, 18, 1680. (d) Vicic, D. A.; Jones, W. D. J. Am. Chem. Soc. 1997, 119, 10855. (e) Vicic, D. A.; Jones, W. D. J. Am. Chem. Soc. 1999, 121, 7606.
17. Several platinacycles (references a-c) and nickelacycles (references d, e) that are closely related to the metallathiabenzenes cited in ref 4 have been reported. However, spectroscopic and structural data suggest that these molecules are better described as metallathiacy-clohexa-1,3-dienes. See: (a) Garcia, J. J.; Mann, B. E.; Adams, H.; Bailey, N. A.; Maitlis, P. M. J. Am. Chem. Soc. 1995, 117, 2179. (b) Garcia, J. J.; Arevalo, A.; Capella, S.; Chehata, A.; Hernandez, M.; Montiel, V.; Picazo, G.; Del Rio, F.; Toscano, R. A.; Adams, H.; Maitlis, P. M. Polyhedron 1997, 16, 3185. (c) Arevalo, A.; Bernes, S.; Garcia, J. J.; Maitlis, P. M. Organometallics 1999, 18, 1680. (d) Vicic, D. A.; Jones, W. D. J. Am. Chem. Soc. 1997, 119, 10855. (e) Vicic, D. A.; Jones, W. D. J. Am. Chem. Soc. 1999, 121, 7606.
18. Several platinacycles (references a-c) and nickelacycles (references d, e) that are closely related to the metallathiabenzenes cited in ref 4 have been reported. However, spectroscopic and structural data suggest that these molecules are better described as metallathiacy-clohexa-1,3-dienes. See: (a) Garcia, J. J.; Mann, B. E.; Adams, H.; Bailey, N. A.; Maitlis, P. M. J. Am. Chem. Soc. 1995, 117, 2179. (b) Garcia, J. J.; Arevalo, A.; Capella, S.; Chehata, A.; Hernandez, M.; Montiel, V.; Picazo, G.; Del Rio, F.; Toscano, R. A.; Adams, H.; Maitlis, P. M. Polyhedron 1997, 16, 3185. (c) Arevalo, A.; Bernes, S.; Garcia, J. J.; Maitlis, P. M. Organometallics 1999, 18, 1680. (d) Vicic, D. A.; Jones, W. D. J. Am. Chem. Soc. 1997, 119, 10855. (e) Vicic, D. A.; Jones, W. D. J. Am. Chem. Soc. 1999, 121, 7606.
19. 3 ligands (vide infra).
20. As shown in Scheme 3, the fluxional processes lead to enantiomeric products in each case (4a → 4a′ and 4b → 4b′).
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25. In solvents other than acetonitrile, the conversion of 6 back to 4 is essentially complete at room temperature. In acetonitrile, a mixture of 4 and 6 (∼50:50) is observed at room temperature.
26. In this reaction, 4 is produced in situ by dissolving the acetonitrile adduct 6 in pentane: see Experimental Section.
27. -: See ref 1.
28. -.
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31. 5a,c
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