Unified view of the interaction of tetrakis(carboxylato)dirhodium(II) with axial donor-acceptor ligands

Organometallics

Volumn 21, Issue 21, 2002, Pages 4303-4305

  Deubel, Dirk V ^a,b  

^a INSTITUTE OF BIOMEDICAL SCIENCES   (Taiwan)

^b ETH ZURICH   (Switzerland)

Author keywords

[No Author keywords available]

Indexed keywords

BENZENE; CATALYSTS; CHEMICAL BONDS; DIMERS; PROBABILITY DENSITY FUNCTION; RHODIUM COMPOUNDS;

LIGANDS;

ORGANOMETALLICS;

EID: 0038109815     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om020285j     Document Type: Article

References (50)

1. URL: http://staff-www.uni-marburg.de/̃deubel.
2. Doyle, M. P.; Forbes, D. C. Chem. Rev. 1997, 97, 911 and references cited therein.
3. (a) Padwa, A.; Snyder, J. P.; Curtis, E. A.; Sheehan, S. M.; Worsencroft, K. J.; Kappe, C. O. J. Am. Chem. Soc. 2000, 122, 8155.
4. (b) Snyder, J. P.; Padwa, A.; Stengel, T.; Arduengo, A. J., III; Jockisch, A.; Kim, H.-J. J. Am. Chem. Soc. 2001, 123, 1131 and references cited therein.
5. (a) Asara, J. M.; Hess, J. S.; Lozada, E.; Dunbar, K. R.; Allison, J. J. Am. Chem. Soc. 2000, 122, 8.
6. (b) Sorasaenee, K.; Galán-Mascarós, J. R.; Dunbar, K. R. Inorg. Chem. 2002, 41, 433.
7. (a) Clarke, M. J.; Zhu, F.; Frasca, D. R. Chem. Rev. 1999, 99, 2511.
8. (b) Sadler, P. Angew. Chem., Int. Ed. 1999, 38, 1512.
9. (a) Cotton, F. A.; Dikarev, E. V.; Stiriba, S.-E. Organometallics 1999, 18, 2724.
10. (b) Cotton, F. A.; Dikarev, E. V.; Petrukhina, M. A. J. Am. Chem. Soc. 2001, 123, 11655 and references cited therein.
11. Cotton, F. A.; Hillard, E. A.; Murillo, C. A. J. Am. Chem. Soc. 2002, 124, 5658.
12. Miyasaka, H.; Campos-Fernandez, C. S.; Clerac, R.; Dunbar, K. R. Angew. Chem., Int. Ed. 2000, 21, 2831.
13. (a) Cotton, F. A.; Feng, X. J. Am. Chem. Soc. 1998, 120, 3387.
14. (b) Rodriguez-Garcia, C.; Gonzales-Blanco, O.; Oliva, A.; Ortuno, R. M.; Branchadell, V. Eur. J. Inorg. Chem. 2000, 1073.
15. Lichtenberger, D. L.; Pollard, J. R.; Lynn, M. A.; Cotton, F. A.; Feng, X. J. Am. Chem. Soc. 2000, 122, 3182.
16. Selected references: (a) Cundari, T. R.; Gordon, M. S. J. Am. Chem. Soc. 1991, 113, 5231.
17. (b) Jacobsen, H.; Ziegler, T. Inorg. Chem. 1996, 35, 775.
18. (c) Vyboishchikov, S. F.; Frenking, G. Chem. Eur. J. 1998, 4, 1428.
19. (d) Boehme, C.; Frenking, G. Organometallics 1998, 17, 5801.
20. (e) Dalmazio, I.; Duante, H. A. J. Chem. Phys. 2001, 115, 1747.
21. 18-23
22. (a) Becke, A. D. Phys. Rev. A 1988, 38, 3098.
23. (b) Perdew, J. P. Phys. Rev. B 1986, 33, 8822.
24. Van Lenthe, E.; Ehlers, A. E.; Baerends, E. J. J. Chem. Phys. 1999, 110, 8943 and references cited therein.
25. Snijders, J. G.; Baerends, E. J.; Vernooijs, P. At. Data Nucl. Tables 1982, 26, 483.
26. Baerends, E. J.; Ellis, D. E.; Ros, P. Chem. Phys. 1973, 2, 41.
27. (a) Bickelhaupt, F. M.; Baerends, E. J. In Reviews in Computational Chemistry; Lipkowitz, K. B., Boyd, D. B., Eds.; VCH: New York, 2000; Vol. 15, p 1.
28. (b) Te Velde, G.; Bickelhaupt, F. M.; Baerends, E. J.; Fonseca Guerra, C.; Van Gisbergen, S. J. A.; Snijders, J. G.; Ziegler, T. J. Comput. Chem. 2001, 22, 931.
29. (a) Ziegler, T.; Rauk, A. Theor. Chim. Acta 1977, 46, 1.
30. (b) Ziegler, T.; Rauk, A. Inorg. Chem. 1979, 18, 1558.
31. (c) Ziegler, T.; Rauk, A. Inorg. Chem. 1979, 18, 1755.
32. Frenking, G.; Fröhlich, N. Chem. Rev. 2000, 100, 717.
33. For recent examples, see: (a) Uddin, J.; Frenking, G. J. Am. Chem. Soc. 2001, 123, 1683.
34. (b) Cedeño, D. L.; Weitz, E. J. Am. Chem. Soc. 2001, 123, 12857.
35. (c) Deubel, D. V. J. Am. Chem. Soc., in press.
36. Bickelhaupt, F. M.; DeKock, R. L.; Baerends, E. J. J. Am. them. Soc. 2002, 124, 1500.
37. Deubel, D. V.; Ziegler, T. Organometallics 2002, 21, 1603.
38. Deubel, D. V. J. Am. Chem. Soc. 2002, 124, 5834.
39. An alternative decomposition scheme is charge decomposition analysis (CDA); for examples, see: (a) Deubel, D. V.; Frenking, G. J. Am. Chem. Soc. 1999, 121, 2021.
40. (b) Deubel, D. V.; Sundermeyer, J.; Frenking, G. J. Am. Chem. Soc. 2000, 122, 10101.
41. (c) Deubel, D. V.; Schlecht, S.; Frenking, G. J. Am. Chem. Soc. 2001, 123, 10085 and references cited therein.
42. Arduengo, A. J., III; Harlow, R. L.; Kline, M. J. Am. Chem. Soc. 1991, 113, 361.
43. 2d symmetry (2a-c); these structures were also obtained by geometry optimizations using selected starting structures of lower symmetry.
44. 1 singlet-triplet splitting of methylene at the BP86 level (15.7 kcal/mol) is larger than the experimental value (9 kcal/mol): McKellar, A. R. W.; Buenker, P. R.; Sears, T. J.; Evenson, K. M.; Saykally, R. J.; Langhoff, S. R. J. Chem. Phys. 1983, 79, 5251.
45. 6a
46. yz, orbitals of the two Rh centers.
47. (a) Deubel, D. V.; Frenking, G.; Senn, H. M.; Sundermeyer, J. Chem. Commun. 2000, 2468.
48. (b) Deubel, D. V. J. Org. Chem. 2001, 66, 3790.
49. The structure of 2a was also optimized at several DFT and ab initio levels of theory using Gaussian 98 (www.gaussian.com) with the SDD ECP and basis set, giving Rh-Rh distances of 2.864 Å (B3PW91), 2.918 Å (B3LYP), and 3.741 Å (MP2), respectively. These results clearly indicate that the metal-metal bond in the hypothetical dimethylene complex is strongly elongated, if not cleaved.
50. Hirshfeld, E. L. Theor. Chim. Acta 1977, 44, 129.