Structural variations in polynuclear copper(II) complexes based on salicylaldimine type ligands along with dicyanamido co-ligand

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• 作者：Saptarshi Biswas ; Ashutosh Ghoshp> ; p>p>ghosh_59@yahoo.comp>
• 关键词：Copper(II) ; Di-Schiff base ligand ; Crystal structure ; Electrochemical behavior
• 刊名：Polyhedron
• 出版年：2012
• 期刊代码：87_02775387
• 类别：ch
• 出版时间：30 May, 2012
• 卷：39
• 期：1
• 页码：31-37
• 文件大小：1134 K

摘要

Two new polynuclear complexes of Cu(II), [(CuLp>1p>)Cu(N₃C₂)₂]_n (dFont">1) and [(CuLp>2p>)₂Cu(N₃C₂)₂]路H₂O (dFont">2), have been synthesized by reacting the 鈥渓igand complexes鈥? [CuLp>1p>] and [CuLp>2p>] respectively with copper perchlorate and sodium dicyanamide (NaN₃C₂) in ethanol-water, where the di-Schiff base ligands H₂Lp>1p> = N,N鈥?bis(salicylidene)-1,3-propanediamine and H₂Lp>2p> = N,N鈥?bis(伪-methylsalicylidene)-1,3-propanediamine. Structural analysis shows that complex dFont">1 is a 2D polymer formed by linking the dinuclear units through a 渭_1,5-dicyanamido bridge. It contains alternating helical chains of P and M types. Complex dFont">2 is a discrete bent trinuclear species where phenoxido groups of two terminal 鈥渓igand complexes鈥?coordinate to a central Cu(II) along with terminally coordinated dicyanamido anions. Both complexes exhibit irreversible reductive Cu(II)/Cu(I) and quasi-reversible oxidative Cu(II)/Cu(III) responses in cyclic voltammetry. The electrochemically generated Cu(I) species for both complexes are unstable and undergo disproportionation to Cup>0p> and Cup>2+p>.