Synthesis and mechanism study of a dimeric tetranuclear carbonate-bridged copper(II) complex resulting from CO2 fixation by controlling O2 concentration |
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| Affiliation: | 1. State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002, China;2. University of Chinese Academy of Sciences, Beijing 100049, China;1. Center for Regional Revitalization in Research and Education, Akita University, 1-1 Tegatagakuen-machi Akita, 010-8502, Japan;2. Graduate School of Engineering Science, Akita University, 1-1 Tegatagakuen-machi Akita, 010-8502, Japan |
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| Abstract: | A dimeric tetranuclear carbonate-bridged Cu(II) complex Cu4(DPA-iBu)4(μ2-CO3)2(MeOH)2]4 + 1 was prepared in-situ through oxidation of Cu(I) species by controlling the concentration of O2 in CO2. Lower concentration of O2 led to the formation of 1 after CO2 fixation but higher would give product as bis-μ2-hydroxo complex Cu(DPA-iBu)(OH)]22 + 2, which was found to be an intermediate to generate trinuclear carbonated complex Cu3(DPA-iBu)3(μ3-CO3)(MeCN)2(H2O)]4 + 3. The mechanism of this reaction was proposed and the nucleophilic attack of μ-peroxo Cu(II) species to CO2 molecules was suggested to be responsible for the generation of 1. |
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