Combined spectroscopic and theoretical evidence for a persistent end-on copper superoxo complex

Angewandte Chemie - International Edition

Volumn 43, Issue 33, 2004, Pages 4360-4363

  Schatz, Markus ^b   Raab, Volker ^a   Foxon, Simon P ^b   Brehm, Georg ^c   Schneider, Siegfried ^c   Reiher, Markus ^d   Holthausen, Max C ^a   Sundermeyer, Jörg ^a   Schindler, Siegfried ^b  

^a PHILIPPS UNIVERSITY MARBURG   (Germany)

^b JUSTUS LIEBIG UNIVERSITY   (Germany)

^c UNIVERSITY OF ERLANGEN NUREMBERG   (Germany)

^d UNIVERSITY OF BONN   (Germany)

Author keywords

Copper; Density functional calculations; Dioxygen ligands; Raman spectroscopy; Tripod ligands

Indexed keywords

CHEMICAL BONDS; COMPLEXATION; RAMAN SCATTERING; SPECTROSCOPIC ANALYSIS;

RAMAN SPLITTING; SUPEROXO COMPLEXES;

COPPER;

AMINE; COPPER; GUANIDINE DERIVATIVE; NITROGEN; OXYGEN;

ARTICLE; CHEMICAL REACTION KINETICS; COMPLEX FORMATION; DECOMPOSITION; DENSITY FUNCTIONAL THEORY; LOW TEMPERATURE; RAMAN SPECTROMETRY; ROOM TEMPERATURE; SOLID STATE; THEORETICAL STUDY; ULTRAVIOLET SPECTROSCOPY;

EID: 4544377572     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200454125     Document Type: Article

References (57)

1. a) K. D. Karlin, A. D. Zuberbühler in Bioinorganic Catalysis, 2nd Ed. (Eds.: J. Reedijk, E. Bouwman), Dekker, New York, 1999, p. 469-534;
2. b) S. Schindler, Eur. J. Inorg. Chem. 2000, 11, 2311-2326;
3. c) A. G. Blackman, W. B. Tolman in Structure & Bonding 97: Metal-Oxo and Metal-Peroxo Species in Catalytic Oxidations (Ed.: B. Meunier), Springer, Berlin, 2000, pp. 179-211;
4. d) E. I. Solomon, P. Chen, M. Metz, S.-K. Lee, A. E. Palmer, Angew. Chem. 2001, 113, 4702-4724; Angew. Chem. Int. Ed. 2001, 40, 4570-4590.
5. d) E. I. Solomon, P. Chen, M. Metz, S.-K. Lee, A. E. Palmer, Angew. Chem. 2001, 113, 4702-4724; Angew. Chem. Int. Ed. 2001, 40, 4570-4590.
6. a) E. A. Lewis, W. B. Tolman, Chem. Rev. 2004, 104, 1047-1076;
7. b) L. M. Mirica, X. Ottenwaelder, T. D. P. Stack, Chem. Rev. 2004, 704, 1013-1045.
8. L. Que, Jr., W. B. Tolman, Angew. Chem. 2002, 114, 1160-1185; Angew. Chem. Int. Ed. 2002, 41, 1114-1137.
9. L. Que, Jr., W. B. Tolman, Angew. Chem. 2002, 114, 1160-1185; Angew. Chem. Int. Ed. 2002, 41, 1114-1137.
10. M. Weitzer, S. Schindler, G. Brehm, S. Schneider, E. Hörmann, B. Jung, S. Kaderli, A. D. Zuberbühler, Inorg. Chem. 2003, 42, 1800-1806.
11. B. A. Jazdzewski, A. M. Reynolds, P. L. Holland, V. G. Young, S. Kaderli, A. D. Zuberbühler, W. B. Tolman, J. Biol. Inorg. Chem. 2003, 5, 1432-1437.
12. K. Komiyama, H. Furutachi, S. Nagatomo, A. Hashimoto, H. Hayashi, S. Fujinami, M. Suzuki, T. Kitagawa, Bull. Chem. Soc. Jpn. 2004, 77, 59-72.
13. K. D. Karlin, N. Wei, B. Jung, S. Kaderli, P. Niklaus, A. D. Zuberbühler, J. Am. Chem. Soc. 1993, 115, 9506-9514.
14. a) J. P. Klinman, Chem. Rev. 1996, 96, 2541-2561;
15. b) J. W. Whittaker, Chem. Rev. 2003, 103, 2347-2363;
16. c) S. T. Prigge, B. A. Eipper, R. E. Mains, L. M. Amzel, Science 2004, 304, 864-867
17. K. Fujisawa, M. Tanaka, Y. Moro-oka, N. Kitajima, J. Am. Chem. Soc. 1994, 116, 12079-12080.
18. a) N. W. Aboelella, E. A. Lewis, A. M. Reynolds, W. W. Brennessel, C. J. Cramer, W. B. Tolman, J. Am. Chem. Soc. 2002, 124, 10660-10661;
19. b) D. J. E. Spencer, N. W. Aboelella, A. M. Reynolds, P. L. Holland, W. B. Tolman, J. Am. Chem. Soc. 2002, 124, 2108-2109.
20. M. Harata, K. Jitsukawa, H. Masuda, H. Einaga, J. Am. Chem. Soc. 1994, 116, 10817-10818.
21. L. M. Berreau, S. Mahapatra, J. A. Halfen, V. G. Young, Jr., W. B. Tolman, Inorg. Chem. 1996, 35, 6339-6342.
22. A. Wada, M. Harata, K. Hasegawa, K. Jitsukawa, H. Masuda, M. Mukai, T. Kitagawa, H. Einaga, Angew. Chem. 1998, 110, 874-875; Angew. Chem. Int. Ed. 1998, 37, 798-799.
23. A. Wada, M. Harata, K. Hasegawa, K. Jitsukawa, H. Masuda, M. Mukai, T. Kitagawa, H. Einaga, Angew. Chem. 1998, 110, 874-875; Angew. Chem. Int. Ed. 1998, 37, 798-799.
24. P. Chaudhuri, M. Hess, T. Weyhermüller, K. Wieghardt, Angew. Chem. 1999, 111, 1165-1168; Angew. Chem. Int. Ed. 1999, 38, 1095-1098.
25. P. Chaudhuri, M. Hess, T. Weyhermüller, K. Wieghardt, Angew. Chem. 1999, 111, 1165-1168; Angew. Chem. Int. Ed. 1999, 38, 1095-1098.
26. P. Chen, D. E. Root, C. Campochiaro, K. Fujisawa, E. I. Solomon, J. Am. Chem. Soc. 2003, 125, 466-474.
27. For qualitative theoretical work see: A. Bérces, Int. J. Quantum Chem. 1997, 65, 1077-1086.
28. a) C. J. Cramer, W. B. Tolman, K. H. Theopold, A. L. Rheingold, Frac. Natl Acad. Sci. USA 2003, 100, 3635-3640;
29. b) D. A. Pantazis, J. W. McGrady, Inorg. Chem. 2003, 42, 7734.
30. S. C. Lee, R. H. Holm, J. Am. Chem. Soc. 1993, 115, 11 789-11 798; M. J. Scott, S. C. Lee, R. H. Holm, Inorg. Chem. 1994, 33, 4651-4662; M. Becker, F. W. Heinemann, S. Schindler, Chem. Eur. J. 1999, 5, 3124-3129.
31. S. C. Lee, R. H. Holm, J. Am. Chem. Soc. 1993, 115, 11 789-11 798; M. J. Scott, S. C. Lee, R. H. Holm, Inorg. Chem. 1994, 33, 4651-4662; M. Becker, F. W. Heinemann, S. Schindler, Chem. Eur. J. 1999, 5, 3124-3129.
32. S. C. Lee, R. H. Holm, J. Am. Chem. Soc. 1993, 115, 11 789-11 798; M. J. Scott, S. C. Lee, R. H. Holm, Inorg. Chem. 1994, 33, 4651-4662; M. Becker, F. W. Heinemann, S. Schindler, Chem. Eur. J. 1999, 5, 3124-3129.
33. M. Schatz, M. Becker, O. Walter, G. Liehr, S. Schindler, Inorg. Chim. Acta 2001, 324, 173-179.
34. V. Raab, J. Kipke, O. Burghaus, J. Sundermeyer, Inorg. Chem. 2001, 40, 6964-6971.
35. S. Schindler, unpublished results.
36. H. Wittmann, V. Raab, A. Schorm, J. Plackmeyer, J. Sundermeyer, Eur. J. Inorg. Chem. 2001, 1937-1948.
37. K. Nakamoto, Infrared and Roman Spectra of Inorganic and Coordination Compounds, part B, 5th ed., Wiley, New York, 1997, p. 97-101.
38. Density functional calculations were performed using the program Turbomolep[27] employing the BP86 functional[28] in combination with the all-electron TZVP basis set of Ahlrichs and co-workers[29] and the resolution of identity (RI) approach.[30] A restricted Kohn-Sham formalism was used throughout. The SNF program package[31] was utilized for numerical evaluation of vibrational frequencies from analytic energy gradients. Starting structures for DFT calculations were generated at the semiempirical PM3(TM) level by means of the program Spartan, which was also used for conformational searching.[32]
39. Conformational searching at the PM3(TM) level[32] revealed a few isoenergetic structures. Reoptimizations of the geometries of selected low-energy conformers at the DFT level resulted in 2 as the most stable conformer. An exhaustive coverage of the conformational space at this level of theory, however, is outside the scope of the present study.
40. The BP86 functional has been identified as a reliable tool for the assessment of structural parameters and vibrational frequencies of transition-metal complexes.[33,34] Although an anharmonic treatment of complexes of the present size is not possible for us, it is generally found that computed harmonic frequencies at the BP86, level compare favorably to experimental fundamentals without scaling.[33] This has been substantiated recently: a) M. Reiher, J. Neugebauer, B. A. Hess, Z. Phys. Chem. (Muenchen Ger.) 2003, 217, 91-103;
41. b) J. Neugebauer, B. A. Hess, J. Chem. Phys. 2003, 118, 7215-7225;
42. c) G. Brehm, M. Reiher, S. Schneider, J. Phys. Chem. A 2002, 106, 12024-12034;
43. d) M. Reiher, G. Brehm, S. Schneider, J. Phys. Chem. A 2004, 108, 734-742.
44. a) 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. Kattanek, A. Köhn, C. Kölmel, M. Kollwitz, K. May, C. Ochsenfeld, H. Öhm, A. Schäfer, U. Schneider, O. Treutler, K. Tsereteli, B. Unterreiner, M. v. Arnim, F. Weigend, P. Weis, H. Weiss, Turbomole - Program System for ab initia Electronic Structure Calculations Version 5.6, Universität Karlsruhe, Germany, 2002;
45. b) R. Ahlrichs in Encyclopedia Computational Chemistry (Ed.: P. v. R. Schleyer), Wiley, Chichester, 1998, p. 3123-3129;
46. c) R. Ahlrichs, M. Bär, M. Häser, H. Horn, C. Kölmel, Chem. Phys. Lett. 1989, 162, 165-169.
47. a) A. D. Becke, Phys. Rev. A 1988, 38, 3098-3100;
48. b) J. B. Perdew, Phys. Rev. B 1986, 33, 8822-8824.
49. A. Schäfer, C. Huber, R. Ahlrichs, J. Chem. Phys. 1994, 100, 5829-5835.
50. a) K. Eichkorn, O. Treutier, H. Öhm, M. Häser, R. Ahlrichs, Chem. Phys. Lett. 1995, 240, 283-289;
51. b) K. Eichkorn, F. Weigend, O. Treutler, R. Ahlrichs, Theor. Chem. Acc. 1997, 97, 119-124;
52. c) R. A. Kendall, H. A. Früchtl, Theor. Chem. Acc. 1997, 97, 158-163.
53. J. Neugebauer, M. Reiher, C. Kind, B. A. Hess, J. Comput. Chem. 2002, 25, 895-910.
54. Spartan, Pro, Wavefunction.
55. W. Koch, M. C. Holthausen, A Chemist's Guide to Density Functional Theory, 2nd Ed., Wiley-VCH, Weinheim, 2001.
56. M. Reiher, O. Salomon, D. Sellmann, B. A. Hess, Chem. Eur. J. 2001, 7, 5195-5202.
57. 2 coincide with the modes identified for the mixed-isotope species, this splitting is unlikely to be of use as a unique signature for end-on complexes.