The first member of a second generation family of ligands derived from metal-ion assisted reactivity of di-2,6-(2-pyridylcarbonyl)pyridine: Synthesis and characterization of a Mn^II/III₄ rhombus

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• 作者：Theocharis C. Stamatatos^a ; ^{thstama@chemistry.upatras.gr} ; Rosa Adam^b ; Catherine P. Raptopoulou^c ; Vassilis Psycharis^c ; Rafael Ballesteros^b ; Belé ; n Abarca^b ; Spyros P. Perlepes^a ; Athanassios K. Boudalis^c ; ^{tbou@ims.demokritos.gr}
• 关键词：Crossed-aldol reactions ; 2 ; 6-Di-(2-pyridylcarbonyl)pyridine ; Ligands' transformation ; Magnetic properties ; Polynuclear manganese complexes ; Reactivity of coordinated ligands
• 刊名：Inorganic Chemistry Communications
• 出版年：2012
• 出版时间：January, 2012
• 年：2012
• 卷：15
• 期：Complete
• 页码：73-77
• 全文大小：541 K

文摘

Nucleophilic attack by the carbanion ^{?/sup>CH₂COCH₃ at the carbonyl carbon atoms of 2,6-di-(2-pyridylcarbonyl)pyridine, pyCOpyCOpy, in the presence of Mnn+ ions under basic conditions has yielded the cationic cluster [Mn₄(OH)₂(L)₂(H₂O)₂](ClO₄)₄ (1), where L2?/sup> is the (py)C(CH₂COCH₃)(O?/sup>)(py)C(CH₂COCH₃)(O?/sup>)(py) dianion. The cluster cation possesses a planar {MnII₂MnIII₂(¦Ì₃-OH)₂(¦Ì-OR)₄}4+ rhombus core, resulting from two ¦Ì₃-OH?/sup> ions and two ¦Ç1:¦Ç2:¦Ç1:¦Ç1:¦Ç1:¦Ç2:¦Ç1:¦Ì₃ bridging L2?/sup> groups from the in situ formed ligand. Complex 1 is antiferromagnetically coupled with an unusual S = 2 ground state resulting from spin frustration effects within the triangular Mn₃ subunits of the cluster.}