Exogenous substrate reactivity with a [Cu(III)2-O2]2+ core: Structural implications [1]

Journal of the American Chemical Society

Volumn 121, Issue 23, 1999, Pages 5583-5584

  Mahadevan, Viswanath ^a   DuBois, Jennifer L ^a   Hedman, Britt ^a,b   Hodgson, Keith O ^a,b   Stack, T D P ^a  

^a STANFORD UNIVERSITY   (United States)

^b SLAC NATIONAL ACCELERATOR LABORATORY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

COPPER COMPLEX; OXYGEN;

CHEMICAL STRUCTURE; COMPLEX FORMATION; FOURIER ANALYSIS; LETTER; REACTION ANALYSIS; SPECTROSCOPY; X RAY ANALYSIS;

EID: 0033575068     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja983635v     Document Type: Letter

References (42)

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17. The potential use of such oxidants in synthesis would be enhanced by the commercial availability of inexpensive ligands.
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23. 2+ complexes do not react significantly (≤2%) with benzyl alcohol at -80 °C or even on warming to 25 °C. (L = N,N′,N,N′-tetramethyl(1R,2R)CHD; N,N′-dimethyl N,N′-diethyl(1R,2R)CHD; N,N′,N,N′-tetraethyl(1R,2R)CHD; N,N′-dimethyl N,N′-dibenzyl(1R,2R)CHD and N,N′,N,N′-tetraethylethylenediamine; CHD = cyclohexanediamine).
24. 1/2 = 12 min) at -10 °C.
25. -1).
26. -1 (Henson, M. J.; Mahadevan, V.; Stack, T. D. P.; Solomon, E. I., unpublished results).
27. (c) Electron paramagnetic resonance data at 77 K indicate a diamagnetic species.
28. (d) Dioxygen binding is irreversible: dioxygen is not displaced upon warming either by evacuation or addition of CO(g).
29. 2), is similar to that of 1 as established by titrations with suitable ferrocene derivatives: ∼2 equiv of decamethylferrocene (-100 mV) are needed to fully quench the LMCT feature at 390 nm.
30. 2.
31. McMillen, D. F.; Golden, D. M. Annu. Rev. Phys. Chem. 1982, 33, 493-532.
32. 2 with 20 equiv of cyclohexadiene or dihydroanthracene at -40 °C for 20 h shows negligible substrate oxidation (<1%).
33. DuBois, J. L.; Mukherjee, P.; Collier, A. M.; Mayer, J. M.; Solomon, E. I.; Hedman, B.; Stack, T. D. P.; Hodgson, K. O. J. Am. Chem. Soc. 1997, 119, 8578-8579.
34. 2. Data were nearly identical within experimental uncertainty for all three samples. Fits to the data produced very similar structural models (See Supporting Information).
35. Backscattenng atoms which differ in Z by 1 are typically not distinguished by EXAFS (e.g., O and N) (Scott, R. A. Methods Enzymol. 1985, 117, 414). For the purposes of calculating phase and amplitude parameters, the copper ligation was modeled by two equivalent O, two equivalent N, and a longer axial O. Separate phase and amplitude parameters were calculated independently for each of these three ligand types. This is the basis for the distinction made between O and N backscatterers in the EXAFS fit to the data.
36. ave = 1.97 Å; Cu-N = 2.25 Å. Results obtained from EXAFS data.
37. Mahapatra, S.; Halfen, J. A.; Wilkinson, E. C; Pan, G. F.; Wang, X. D.; Young, V. G.; Cramer, C. J.; Que, L., Jr.; Tolman, W. B. J. Am. Chem. Soc. 1996, 118, 11555-11574.
38. 4] (∼60%).
39. 2).
40. See Supporting Information.
41. 1/2 for decay of 2 at -40 °C ∼5 h. The oxidation of benzyl alcohol proceeds at -80 °C in the presence of 1.0 equiv of triethylamine in ∼3 h (>48 h in the absence of the amine).
42. Salvato, B.; Santamaria, M.; Beltramini, M.; Alzuet, G.; Casella, L. Biochemistry 1998, 37, 14065-14077.