Unusual N-oxide formation in the peroxidation of cobalt(ii) ethylenediaminetetraacetates
Yu-Chen Yang1, Rui Wu2, Yan Cai2
1Shaanxi Key Laboratory of Natural Products & Chemical Biology, College of Chemistry & Pharmacy, Northwest A&F University, Yangling 712100, People's Republic of China and State Key Laboratory of Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, People's Republic of China. zhzhou@xmu.edu.cn.
Abstract:
Unlike the usual formations of peroxo and superoxo cobalt products as oxygen carriers, N-oxido cobalt(ii) ethylenediaminetetraacetates K4[Co2(edtaO2)2]·nH2O [n = 6.5 (1), 10 (2), H4edta = ethylenediaminetetraacetic acid, C10H16O8N2] and their aggregate [Co2(edtaO2)(H2O)6]n·2nH2O (3) were obtained as dioxygen insertion products. The cobalt ions in dimers 1 and 2 are hexa-coordinated by two edtaO2 ligands in different configurations respectively, which is attributed to the packing of an interesting (H2O)12 water cluster in 2. Further reaction of K4[Co2(edtaO2)2]·nH2O with hydrogen peroxide results in the final trivalent cobalt ethylenediaminetetraacetate K[Co(edta)]·2H2O (4). A water-soluble coordination polymer Na2n[Co(edta)]n·4nH2O (5) was also obtained with a one dimensional zigzag structure. Bond valence calculation is consistent with the products 1-5.
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