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35348814518
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note
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The 1H-NMR spectrum of 2,2′-bipyridyl-6,6′-diacid chloride was published [28].
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95
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35348913314
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note
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Macrocycle 4 can be obtained from pure starting bipyridine derivatives. To obtain pure 2,2′-bipyridyl-6,6′-diacid chloride, pure 2,2′-bipyridyl-6,6′-diacid have to be synthesized. Thus, 2,2′-bipyridyl-6,6′-dimethylester was synthesized, because this compound has the higher solubility and it is easy to purify by column chromatography (silica-gel). After purification, 2,2′-bipyridyl-6,6′-dimethyl-ester was converted to 2,2′-bipyridyl-6,6′-diacid by hydrolysis. 1H-NMR data of 2,2′-bipyridyl-6,6′-dimethylester (CDCl3) δ 8.751 (H5, d), 8.172 (H3, d), 8.006 (H4, t).
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97
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35348898573
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note
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5IO was carried out under the reaction conditions of the previously works [18-20].
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98
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35348815111
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note
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When norbornene oxidation was carried out in the presence of imidazole, the ratio of norbornene oxide and the total yield increased from 24% to 55% and from 88% to 100%, respectively. It has been reported that the effect of the donor ligand as the cocatalyst is not observed for the salen Mn complexes [21b]. The difference in the reactivity to donor ligand would be dependent upon the character of oxometal. In the case of complex 4, it leaves unanswered the question of whether the product formed by the reaction of oxo-Mn with alkene is cationic intermediate or radical intermediate.
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101
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35348926175
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The detailed results about this cyclic voltammetry will be published in the future, 2005.
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102
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35348847317
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note
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5IO) are added.
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105
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35348873927
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note
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The yields of hydrocarbon oxidation by 4 are considered to be higher than the yields reported in previous papers using the Mn complexes [16,17,21].
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106
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35348927048
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note
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To confirm the reliability of the results obtained with complex 4, the oxidation of benzene was carried out by using tetrakis(2,6-dichlorophenyl)porphyrin Mn complex as the catalyst under the same condition. However, the oxidation products such as phenol and 1,4-benzoquinone were not observed.
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-
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107
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35348841682
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note
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The trials of structural characterization of X-ray crystallography of the intermediates formed from complexes 2 and 4 were unsuccessful, because these intermediates were too unstable to isolate as a single crystal.
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