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Volumn 130, Issue 29, 2008, Pages 9514-9523

Dioxygen activation at a mononuclear Cu(I) center embedded in the calix[6]arene-tren core

Author keywords

[No Author keywords available]

Indexed keywords

ARSENIC COMPOUNDS; COPPER; COPPER ALLOYS; METALS;

EID: 47749131243     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja8019406     Document Type: Article
Times cited : (66)

References (70)
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    • Special issue on dioxygen activation by
    • Special issue on dioxygen activation by metalloenzymes and models. Acc. Chem. Res. 2007, 40, 465-634.
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    • metalloenzymes1    models2
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    • (b) Klinman, J. P. Chem. Rev. 1996, 96, 2541-2562.
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    • Recent reviews on Cu-enzyme modeling:(a) Hatcher, L. Q.; Karlin, K. D. J. Biol. Inorg. Chem. 2004, 9, 669-683.
    • Recent reviews on Cu-enzyme modeling:(a) Hatcher, L. Q.; Karlin, K. D. J. Biol. Inorg. Chem. 2004, 9, 669-683.
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    • For recent communications related to reactive mononuclear copper species, see: a
    • For recent communications related to reactive mononuclear copper species, see: (a) Hong, S.; Huber, S. M.; Gagliardi, L.; Cramer, C. C.; Tolman, W. B. J. Am. Chem. Soc. 2007, 129, 14190-14192.
    • (2007) J. Am. Chem. Soc , vol.129 , pp. 14190-14192
    • Hong, S.1    Huber, S.M.2    Gagliardi, L.3    Cramer, C.C.4    Tolman, W.B.5
  • 31
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    • For Cu(tren) chemistry, see:(a) Becker, M.; Heinemann, F. W.; Schindler, S. Chem.-Eur. J. 1999, 3124-3129.
    • For Cu(tren) chemistry, see:(a) Becker, M.; Heinemann, F. W.; Schindler, S. Chem.-Eur. J. 1999, 3124-3129.
  • 43
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    • Harrowfield, J, Vicens, J, Eds, Springer: Dordrecht, Holland, Chapter 13
    • Reinaud, O.; Le Mest, Y.; Jabin, I. In Calixarenes in The Nanoworld; Harrowfield, J., Vicens, J., Eds.; Springer: Dordrecht, Holland, 2006; Chapter 13.
    • (2006) Calixarenes in The Nanoworld
    • Reinaud, O.1    Le Mest, Y.2    Jabin, I.3
  • 44
    • 0032538471 scopus 로고    scopus 로고
    • Calix[6]arene-based tris(pyridine) system: (a) Blanchard, S.; Le Clainche, L.; Rager, M.-N.; Chansou, B.; Tuchagues, J. P.; Duprat, A.; Le Mest, Y.; Reinaud, O. Angew. Chem., Int. Ed. 1998, 37, 2732-2735.
    • Calix[6]arene-based tris(pyridine) system: (a) Blanchard, S.; Le Clainche, L.; Rager, M.-N.; Chansou, B.; Tuchagues, J. P.; Duprat, A.; Le Mest, Y.; Reinaud, O. Angew. Chem., Int. Ed. 1998, 37, 2732-2735.
  • 47
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    • Calix[6]arene-based tris(imidazole) system: (a) Rondelez, Y.; Sénèque, O.; Rager, M.-N.; Duprat, A. F.; Reinaud, O. Chem.-Eur. J. 2000, 6, 4218-4226.
    • Calix[6]arene-based tris(imidazole) system: (a) Rondelez, Y.; Sénèque, O.; Rager, M.-N.; Duprat, A. F.; Reinaud, O. Chem.-Eur. J. 2000, 6, 4218-4226.
  • 54
    • 47749122951 scopus 로고    scopus 로고
    • R,R′ stands for a tren ligand with R and R′ N-substituents.
    • R,R′ stands for a tren ligand with R and R′ N-substituents.
  • 56
    • 85153252494 scopus 로고    scopus 로고
    • For the host properties of CalixtrenZn(II) complexes, see: (a) Darbost, U.; Zeng, X.; Rager, M.-N.; Giorgi, M.; Jabin, I.; Reinaud, O. Eur. J. Inorg. Chem. 2004, 4371-4374.
    • For the host properties of CalixtrenZn(II) complexes, see: (a) Darbost, U.; Zeng, X.; Rager, M.-N.; Giorgi, M.; Jabin, I.; Reinaud, O. Eur. J. Inorg. Chem. 2004, 4371-4374.
  • 60
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    • For a mechanistic study with various alkylhalides, see: b
    • For a mechanistic study with various alkylhalides, see: (b) Osako, T.; Karlin, K. D.; Itoh, S. Inorg. Chem. 2005, 44, 410-415.
    • (2005) Inorg. Chem , vol.44 , pp. 410-415
    • Osako, T.1    Karlin, K.D.2    Itoh, S.3
  • 63
    • 0035451497 scopus 로고    scopus 로고
    • BMPO was used because it is a good radical trap for superoxide but does not react with carboradicals. The signal attribution to adducts A and B has been further substantiated by comparison to the signals recorded from a solution of BMPO in dry MeCN containing various bases or acids (such as trifluoroacetic acid, triethylamine, lutidine, to which KO2 and crown ether (8-C6) have been added. See: Zhao, H, Joseph, J, Zhang, H, Karoui, H, Kalyanaraman, B. Free Radical Biol. Med. 2001, 31, 599-606
    • 2 and crown ether (8-C6) have been added. See: Zhao, H.; Joseph, J.; Zhang, H.; Karoui, H.; Kalyanaraman, B. Free Radical Biol. Med. 2001, 31, 599-606.
  • 64
    • 47749135257 scopus 로고    scopus 로고
    • The same procedure carried out with the reaction products resulting from the reaction in MeCN showed unmodified Calixtren ligand a nice sharp 1H spectrum attesting to a C3v symmetrical calixarene core, See Figure S1
    • 3v symmetrical calixarene core). See Figure S1.
  • 65
    • 47749142070 scopus 로고    scopus 로고
    • + + O.
    • + + O.
  • 66
    • 47749129623 scopus 로고    scopus 로고
    • Oxygenation in α-position of the nitrogen atom would lead to an amido function (for the M + 14 product), which would strongly change the coordination environment of the Cu center. Most consistent is the formation of an ester moiety in β-position, which indeed should be quite sensitive to acid-base treatments.
    • Oxygenation in α-position of the nitrogen atom would lead to an amido function (for the M + 14 product), which would strongly change the coordination environment of the Cu center. Most consistent is the formation of an ester moiety in β-position, which indeed should be quite sensitive to acid-base treatments.
  • 67
    • 47749093149 scopus 로고    scopus 로고
    • The cuprous complex with an empty cavity, CalixtrenCu 1(Ø, whose existence in a 1:1 ratio in pure MeCN at RT has been established by 1H NMR spectroscopy (see ref 35) is not detected under these experimental conditions, due to fast binding/unbinding of MeCN relative to the CV scan rate (see ref 33, However, the fact that only 70% of the Cu(II) complex is recovered in this experiment carried out at RT, as compared to the ca. 100% yield in the above-described experiment run at low T, is assignable to the enthalpically favored presence of MeCN in the calixarene pocket
    • 1H NMR spectroscopy (see ref 35) is not detected under these experimental conditions, due to fast binding/unbinding of MeCN relative to the CV scan rate (see ref 33). However, the fact that only 70% of the Cu(II) complex is recovered in this experiment carried out at RT, as compared to the ca. 100% yield in the above-described experiment run at low T, is assignable to the enthalpically favored presence of MeCN in the calixarene pocket.
  • 68
    • 33845283334 scopus 로고    scopus 로고
    • Passivation of the Pt electrode is also observed when H2O 2 is added to the MeCN solution of the complex. Thus, it might be related to the disproportionation of O2, that is released at the electrode during the reaction with O2. See:(a) Andrieux, C. P, Hapiot, P, Savéant, J.-M. J. Am. Chem. Soc. 1987, 109, 3768-3775, and refs cited therein
    • 2. See:(a) Andrieux, C. P.; Hapiot, P.; Savéant, J.-M. J. Am. Chem. Soc. 1987, 109, 3768-3775, and refs cited therein.
  • 69
    • 47749104125 scopus 로고    scopus 로고
    • It has been shown for the closely related tris(pyridine) system that the relative affinity of the Cu(I) center embedded in a hexa(tBu, calix[6]arene cavity for PhCN versus MeCN is 1/500 due to its weaker binding ability and its larger size see ref 29b
    • tBu)- calix[6]arene cavity for PhCN versus MeCN is 1/500 due to its weaker binding ability and its larger size (see ref 29b).
  • 70
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    • -1.
    • -1.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.