Mechanism of oxidation of (olefin)RhI and -IrI complexes by H2O2

European Journal of Inorganic Chemistry

Volumn , Issue 11, 2004, Pages 2385-2391

  Budzelaar, Peter H M ^a   Blok, Arno N J ^a  

^a RADBOUD UNIVERSITY NIJMEGEN   (Netherlands)

Author keywords

Density functional calculations; Iridium; Oxidation; Oxygenation; Rhodium

Indexed keywords

CYCLIZATION; DENSITY FUNCTIONAL THEORY; ETHERS; IRIDIUM; IRIDIUM COMPOUNDS; OXIDATION; RHODIUM COMPOUNDS;

CYCLIZATIONS; DENSITY-FUNCTIONAL CALCULATIONS; DFT STUDY; HETEROLYTIC CLEAVAGE; OLEFIN OXIDATION; OXETANES;

OLEFINS;

ALKENE DERIVATIVE; ETHER DERIVATIVE; HYDROGEN PEROXIDE; IRIDIUM COMPLEX; OXETANE DERIVATIVE; RHODIUM COMPLEX;

ARTICLE; CHEMICAL BOND; CYCLIZATION; DENSITY FUNCTIONAL THEORY; OXIDATION; PROTON TRANSPORT; THERMODYNAMICS;

EID: 4544266386     PISSN: 14341948     EISSN: None     Source Type: Journal    
DOI: 10.1002/ejic.200300546     Document Type: Article

References (40)

1. B. de Bruin, M. J. Boerakker, J. J. J. M. Donners, B. E. C. Christiaans, P. P. J. Schlebos, R. de Gelder, J. M. M. Smits, A. L. Spek, A. W. Gal, Angew. Chem. Int. Ed. Engl. 1997, 36, 2064.
2. T. C. Flood, M. Iimura, J. M. Perotti, A. L. Rheingold, T. E. Concolino, Chem. Commun. 2000, 1681.
3. B. de Bruin, J. A. Brands, J. J. J. M. Donners, M. P. J. Donners, R. de Gelder, J. M. M. Smits, A. W. Gal, A. L. Spek, Chem. Eur. J. 1999, 5, 2921.
4. R. J. N. A. M. Kicken, PhD Thesis, Nijmegen, 2001.
5. M. Krom, PhD Thesis, Nijmegen, 2003.
6. B. de Bruin, M. J. Boerakker, R. de Gelder, J. M. M. Smits, A. W. Gal, Angew. Chem. Int. Ed. 1999, 38, 219.
7. B. de Bruin, M. J. Boerakker, J. A. W. Verhagen, R. de Gelder, J. M. M. Smits, A. W. Gal, Chem. Eur. J. 2000, 6, 298.
8. B. de Bruin, J. A. W. Verhagen, C. H. J. Schouten, A. W. Gal, D. Feichtinger, D. A. Plattner, Chem. Eur. J. 2001, 7, 416.
9. V. W. Day, W. G. Klemperer, S. P. Lockledge, D. J. Main, J. Am. Chem. Soc. 1990, 112, 2033.
10. 2 as the actual oxidant of the olefin complex (as suggested in ref.[11]).
11. B. de Bruin, T. P. J. Peters, J. B. M. Wilting, S. Thewissen, J. M. M. Smits, A. W. Gal, Eur. J. Inorg. Chem. 2002, 2671.
12. 2O, all relevant transition states were found.
13. See, for example: T. Cundari, Chem. Rev. 2000, 100, 807 and references cited therein.
14. The "transition state energies" given in Scheme 5 for displacement of a COD C=C bond by a picolyl group represent the energies of hypothetical 16e intermediates having both the picolyl group and the C=C bond detached from the metal atom.
15. See, for example: [15a] Y.-D. Wu, D. K. W. Lai, J. Org. Chem. 1995, 60, 673.
16. [15b] Y.-D. Wu, D. K. W. Lai, J. Am. Chem. Soc. 1995, 117, 11327.
17. [15c] I. V. Yudanov, P. Gisdakis, C. di Valentin, N. Rösch, Eur. J. Inorg. Chem. 1999, 2135.
18. See, for example: [16a] I. V. Yudanov, C. di Valentin, P. Gisdakis, N. Rösch, J. Mol. Catal. 2000, A158, 189.
19. [16b] D. V. Deubel, J. Sundermeyer, G. Frenking, J. Am. Chem. Soc. 2000, 122, 10101.
20. [16c] D. V. Deubel, J. Sundermeyer, G. Frenking, Inorg. Chem. 2000, 39, 2314.
21. [16d] D. V. Deubel, J. Sundermeyer, G. Frenking, Eur. J. Inorg. Chem. 2001, 1819.
22. IV-catalysed epoxidation: [17a] D. Tantanak, M. A. Vincent, I. H. Hillier, Chem. Commun. 1998, 1031. However, a later solvation study did not show any specific effect of hydrogen bonding on the ease of oxygen transfer:
23. [17b] R. R. Sever, T. W. Root, J. Phys. Chem. 2003, B107, 4090.
24. See also: B. de Bruin, P. H. M. Budzelaar, A. W. Gal, Angew. Chem., accepted.
25. [19a] R. Ahlrichs, M. Bär, H.-P. Baron, R. Bauernschmitt, S. Böcker, M. Ehrig, K. Eichkorn, S. Elliott, F. Furche, F. Haase, M. Häser, C. Hättig, H. Horn, C. Huber, U. Huniar, M. Kattannek, A. Köhn, C. Kölmel, M. Kollwitz, K. May, C. Ochsenfeld, H. Öhm, A. Schäfer, U. Schneider, O. Treutler, K. Tsereteli, B. Unterreiner, M. von Arnim, F. Weigend, P. Weis, H. Weiss, Turbomole, version 5, Theoretical Chemistry Group, University of Karlsruhe, January 2002.
26. [19b] O. Treutler, R. Ahlrichs, J. Chem. Phys. 1995, 102, 346.
27. [19c] Turbomole basis set library, Turbomole, version 5, see ref.[12a]
28. [19d] A. Schäfer, H. Horn, R. Ahlrichs, J. Chem. Phys. 1992, 97, 2571.
29. [19e] D. Andrae, U. Haeussermann, M. Dolg, H. Stoll, H. Preuss, Theor. Chim. Acta 1990, 77, 123.
30. [19f] A. Schäfer, C. Huber, R. Ahlrichs, J. Chem. Phys. 1994, 100, 5829.
31. [20a] PQS, version 2.4, Parallel Quantum Solutions, Fayetteville, Arkansas, USA, 2001 (the Baker optimiser is available separately from PQS upon request).
32. [20b] J. Baker, J. Comput. Chem. 1986, 7, 385.
33. [21a] A. D. Becke, Phys. Rev. A 1988, 38, 3089.
34. [21b] J. P. Perdew, Phys. Rev. B 1986, 33, 8822.
35. K. Eichkorn, F. Weigend, O. Treutler, R. Ahlrichs, Theor. Chem. Acc. 1997, 97, 119.
36. [23a] C. Lee, W. Yang, R. G. Parr, Phys. Rev. B 1988, 37, 785.
37. [23b] A. D. Becke, J. Chem. Phys. 1993, 98, 1372.
38. [23c] A. D. Becke, J. Chem. Phys. 1993, 98, 5648.
39. [23d] All calculations were performed using the Turbomole functional "b3-lyp", which is not the same as the Gaussian "B3LYP" functional.
40. A. Klamt, G. Schüürmann, J. Chem. Soc., Perkin Trans. 2 1993, 799.