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Electrochemical properties of uranium(VI) complexes with multidentate ligands in $$N,N$$-dimethylformamide

$$N,N$$-ジメチルホルムアミド溶媒中のU(VI)錯体に関する電気化学的研究

Kim, S.-Y.; 朝倉 俊英; 森田 泰治  ; 池田 泰久*

Kim, S.-Y.; Asakura, Toshihide; Morita, Yasuji; Ikeda, Yasuhisa*

$$N,N$$-ジメチルホルムアミド溶媒中のUO$$_{2}$$($$beta$$-diketonato)$$_{2}$$DMF, UO$$_{2}$$(trop)$$_{2}$$DMF及びUO$$_{2}$$(sap)(DMF)$$_{2}$$, (DMF=$$N,N$$-dimethyl formamide, $$beta$$-diketonate=thenoyltrifluoroacetonate(ttfa), benzoyl trifluoroacetonate(btfa), and dibenzoylmethanate(dbm), trop=tropolonate, and sap=2-salicylidenaminophenolate)錯体について、サイクリックボルタンメトリー法を用いて電気化学的研究を行った。その結果、形式電位(E$$^{o}$$, ${it vs}$.フェロセン/フェロセニウム)はUO$$_{2}$$(ttfa)$$_{2}$$DMF錯体(-1.176V),UO$$_{2}$$(btfa)$$_{2}$$DMF錯体(-1.183V),UO$$_{2}$$(dbm)$$_{2}$$DMF錯体(-1.461V),UO$$_{2}$$(trop)$$_{2}$$DMF錯体(-1.456V)及びUO$$_{2}$$(sap)(DMF)$$_{2}$$錯体(-1.585V)であった。これらの錯体は準可逆的にU(V)に還元され、多座配位子を有する錯体ほど、形式電位はより負側にシフトすることがわかった。以上の結果から、単座配位子を持つウラニル錯体よりも多座配位子を持つウラニル錯体の方が、安定なU(V)錯体を生成することが確認された。

The electrochemical reactions of UO$$_{2}$$($$beta$$-diketonato)$$_{2}$$DMF, UO$$_{2}$$(trop)$$_{2}$$DMF and UO$$_{2}$$(sap)(DMF)$$_{2}$$, (DMF = N,N-dimethylformamide, $$beta$$-diketonate = thenoyltrifluoroacetonate (ttfa), benzoyltrifluoroacetonate (btfa), and dibenzoylmethanate(dbm), trop = tropolonate, and sap = 2-salicylidenaminophenolate) complexes in DMF solution containing tetrabutyl ammonium perchlorate as a supporting electrolyte have been studied with cyclic voltammetry. These uranyl(VI) complexes were found to be quasi-reversibly reduced to U(V) species. The formal redox potentials (E$$^{o}$$, ${it vs}$. ferrocene/ferrocenium) for U(VI)/U(V) couples were determined to be -1.18 V for UO$$_{2}$$(ttfa)$$_{2}$$DMF, -1.18 V for UO$$_{2}$$(btfa)$$_{2}$$DMF, -1.46 V for UO$$_{2}$$ (dbm)$$_{2}$$DMF, -1.46 V for UO$$_{2}$$(trop)$$_{2}$$DMF, and -1.59 V for UO$$_{2}$$(sap)(DMF)$$_{2}$$.

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パーセンタイル:50.75

分野:Chemistry, Physical

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