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R,R′ stands for a tren ligand with R and R′ N-substituents.
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R,R′ stands for a tren ligand with R and R′ N-substituents.
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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.
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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
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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.
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64
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47749135257
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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.
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65
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47749142070
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+ + O.
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+ + O.
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66
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47749129623
-
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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.
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67
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47749093149
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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
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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.
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68
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33845283334
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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
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2. See:(a) Andrieux, C. P.; Hapiot, P.; Savéant, J.-M. J. Am. Chem. Soc. 1987, 109, 3768-3775, and refs cited therein.
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69
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47749104125
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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
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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).
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70
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47749127313
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-1.
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