Role of Redox-Inactive Metal Ions in Modulating the Reduction Potential of Uranyl Schiff Base Complexes: Detailed Experimental and Theoretical Studies
作者:Tanmoy Kumar Ghosh、Souvik Maity、Soumavo Ghosh、Rosa M. Gomila、Antonio Frontera、Ashutosh Ghosh
DOI:10.1021/acs.inorgchem.2c00645
日期:2022.5.9
mononuclear uranyl complex, [UO2L] (1), has been synthesized with the ligand N,N′-bis(3-methoxy-2-hydroxybenzylidene)-1,6-diamino-3-azahexane (H2L). The complex showed a reversible U(VI)/U(V) redox couple in cyclic voltammetric measurements. The reduction potential of this couple showed a positive shift upon the addition of redox-inactive alkali- and alkaline-earth Lewis acidic metal ions (Li+, Na+,
用配体N , N '-bis(3-methoxy-2-hydroxybenzylidene)-1,6-diamino-3-aza己烷 (H 2 L)合成了单核铀酰配合物 [UO 2 L] ( 1 ) . 该复合物在循环伏安测量中显示出可逆的 U(VI)/U(V) 氧化还原对。在添加氧化还原惰性的碱金属和碱土路易斯酸性金属离子(Li +、Na +、K +、Ca 2+、Sr 2+和 Ba 2+)后,这对离子对的还原电位显示出正移配合物1的乙腈溶液. 还原电位的正移是基于路易斯酸度和相应金属离子的内电场效应来解释的。双金属配合物 [UO 2 LLi(NO 3 )] ( 2 ), [UO 2 LNa(BF 4 )] 2 ( 3 ), [UO 2 LK(PF 6 )] 2 ( 4 ), [(UO 2 L) 2 Ca]·(ClO 4 ) 2 ·CH 3 CN ( 5 ), [(UO 2 L) 2 Sr(H