Reversible cleavage and formation of the dioxygen O-O bond within a dicopper complex

Science

Volumn 271, Issue 5254, 1996, Pages 1397-1400

  Halfen, Jason A ^a   Mahapatra, Samiran ^a   Wilkinson, Elizabeth C ^a   Kaderli, Susan ^b   Young Jr , Victor G ^a   Que Jr , Lawrence ^a   Zuberbühler, Andreas D ^b   Tolman, William B ^a  

^a University of Minnesota   (United States)

^b UNIVERSITY OF BASEL   (Switzerland)

Author keywords

[No Author keywords available]

Indexed keywords

COPPER COMPLEX; IRON COMPLEX; MANGANESE; OXYGEN; WATER;

ARTICLE; CHEMICAL BOND; CRYSTALLOGRAPHY; KINETICS; OXIDATION; PHOTOSYNTHESIS; PRIORITY JOURNAL; REDUCTION; SPECTROSCOPY;

EID: 0030005669     PISSN: 00368075     EISSN: None     Source Type: Journal    
DOI: 10.1126/science.271.5254.1397     Document Type: Article

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26. 2.
27. 3, number of formula units per cell, Z = 8. Refinement of 523 variables based on 7863 reflections and 112 restraints converged at R1 = 0.1012 and weighted R2 = 0.2523 for data with reflection intensities 1 > 2σ(l) using SHELXTL 5 0
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30. 2+ unit, which is produced upon its decomposition (9, 19) Experimental assignment of the Cu oxidation state in 2 and 3 is difficult on the basis of the available data; a molecular orbital picture of the bonding in their cores derived from ab initio calculations (9) that avoids formal charge assignments may be most appropriate.
31. D = 34 at -5O°C; 11 at 25°C) The temperature dependence of the KIE is consistent with a tunneling contribution to the reaction rate, similar to that observed for the decomposition of 3 (9) and a previously reported peroxo-dicobalt complex [O. M. Reinaud and K. H. Theopold, J Am Chem Soc. 116, 6979 (1994)].
32. D = 34 at -5O°C; 11 at 25°C) The temperature dependence of the KIE is consistent with a tunneling contribution to the reaction rate, similar to that observed for the decomposition of 3 (9) and a previously reported peroxo-dicobalt complex [O. M. Reinaud and K. H. Theopold, J Am Chem Soc. 116, 6979 (1994)].
33. 2, followed by a fast irreversible step. At higher temperatures, incomplete adduct formation, secondary decay, and significantly changing spectra precluded simple numerical treatment. In all the kinetic experiments we used a modified SFL-21 low-temperature stopped flow unit (508 diodes, 1.3-ms minimum integration time, spectral range of 300 to 720 nm) and we analyzed the results using the program KINFIT For further details, see (22).
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38. 2 have been reported: J A Gilbert et al., ibid. 107, 3855 (1985); D Geselowitz and T J Meyer, Inorg. Chem. 29, 3894 (1990); R. Ramaraj, A. Kira, M. Kaneko, Angew. Chem., Int. Ed Engl 25, 825 (1986); Y. Naruta, M. Sasayama, T. Sasaki, ibid. 33, 1839 (1994); M. Watkinson, A Whiting, C. A McAuliffe, J Chem. Soc. Chem. Commun 1994, 2141 (1994).
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40. 2 have been reported: J A Gilbert et al., ibid. 107, 3855 (1985); D Geselowitz and T J Meyer, Inorg. Chem. 29, 3894 (1990); R. Ramaraj, A. Kira, M. Kaneko, Angew. Chem., Int. Ed Engl 25, 825 (1986); Y. Naruta, M. Sasayama, T. Sasaki, ibid. 33, 1839 (1994); M. Watkinson, A Whiting, C. A McAuliffe, J Chem. Soc. Chem. Commun 1994, 2141 (1994).
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42. This research was supported by the Searle Scholars Program Chicago Community Trust (WBT.), the Camille and Henry Dreyfus and Sloan Foundations (fellowships to W.B.T.), the National Science Foundation (National Young Investigator Award to W.B T), the National Institutes of Health (grant GM33162 to L.Q., grant GM47365 toW.B.T., and a predoctororal traineeship to E.C.W.), the University of Minnesota (Doctoral Dissertation Fellowship to J.A.H.), and the Swiss National Science Foundation (A.D.Z.).