Hexaazamacrocyclic Nickel and Copper Complexes and their Reactivity with Tetracyanoquinodimethane

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• 作者：Loreto Ballester ; Angel Gutié ; rrez ; M. Felisa Perpiñ ; &aacute ; n ; Ana E. S&aacute ; nchez ; Marina Fonari ; Maria Gdaniec
• 刊名：Inorganic Chemistry
• 出版年：2007
• 出版时间：May 14, 2007
• 年：2007
• 卷：46
• 期：10
• 页码：3946 - 3955
• 全文大小：480K
• 年卷期：v.46,no.10(May 14, 2007)
• ISSN：1520-510X

文摘

The hexaazamacrocycle 1,4,7,10,13,16-hexaazacyclooctadecane, [18]ane-N<SUB>6, forms mono- and dinuclear derivativeswith copper chloride depending on the reaction stoichiometries and times. The mononuclear derivative, [Cu([18]ane-N₆)]Cl₂·H₂O, presents the macrocycle wrapped around the metal atom in a distorted octahedral coordinativeenvironment, while the dinuclear derivative, [Cu₂([18]ane-N₆)Cl₂]Cl₂·4H₂O, is formed by a central Cu₂Cl₂ coresurrounded by an almost planar macrocycle. The crystal structure of both derivatives is stabilized by a network ofhydrogen bonds involving the amine macrocyclic groups, the chloride anions, and the crystallization water molecules.The copper atoms in the dinuclear derivative show a strong antiferromagnetic coupling, as expected for the crystalstructure parameters. A mononuclear nickel derivative has also been obtained from nickel nitrate by following thesame synthetic procedure. These compounds react with TCNQ salts with formation of two types of derivatives,[M([18]ane-N₆)](TCNQ)₂ and [M([18]ane-N₆)](TCNQ)₄, depending on the use of radical-anionic or mixed-valenceTCNQ salts in the reaction. The crystal structures of the nickel derivatives show that the former derivatives arebuilt up by macrocyclic metal cations surrounded by dimeric dianions (TCNQ)₂^2-, either isolated or stacked alongthe crystal. The derivative with four TCNQ units/formula consists of alternated chains of metallomacrocyclic cationsand stacked TCNQ anions. The crystal parameters suggest that every TCNQ holds approximately 0.5 electronsand overlaps with a neighboring unit to form dimeric monoanions, (TCNQ)₂^-.