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• 作者：E.A. Goreshnik^a ; ^{evgeny.goreshnik@ijs.si} ; A.A. Vakulka^a ; Yu. I. Slyvka^b ; M.G. Mys'kiv^b
• 关键词：Copper ; Coordination chemistry ; Heterocycles ; 畏2-Interaction
• 刊名：Journal of Organometallic Chemistry
• 出版年：2012
• 期刊代码：64_0022328x
• 类别：ch
• 出版时间：1 July, 2012
• 卷：710
• 期：Complete
• 页码：1-5
• 文件大小：405 K

摘要

The alternating current electrochemical synthesis starting from ethanol solution of Cu(ClO₄)₂路6H₂O, CuSO₄路5H₂O and Cu(BF₄)₂路6H₂O with the equimolar mixture of 1- and 2-allylbenzotriazole (all-bta) has led to a formation of Cu[2-all-bta]ClO₄ (I), Cu[2-all-bta]HSO₄ (II) and Cu[2-all-bta]BF₄路H₂O (III) compounds. The direct interaction between Cu(ClO₄)₂路6H₂O and the mixture of 1- and 2-allylbenzotriazole in ethanol solution results in an appearance of Cu[(1-all-bta)(2-all-bta)]ClO₄ (IV) compound. These results are strikingly different from earlier performed syntheses using the same ligands mixture and copper(II) halides, and producing coordination compounds with 1-allylbenzotriazole only. Compounds I and II are isotypical and crystallize in a monoclinic space group Cc. I: a聽=聽9.5413(10)聽脜, b聽=聽12.3171(9)聽脜, c聽=聽10.3264(10)聽脜, 尾聽=聽111.155(4)掳, V聽=聽1131.78(18)聽脜³, Z聽=聽4. II: a聽=聽9.1707(17)聽脜, b聽=聽13.6639(17)聽脜, c聽=聽9.4543(17)聽脜, 尾聽=聽105.555(7)掳, V聽=聽1141.3(3)聽脜³, Z聽=聽4. The main feature of structures I and II is a chelate-bridging role of the ligand moiety, bonded to one copper ion via CC-bond of the allyl group and nitrogen atom of the triazole core, and to the second Cu⁺ centre by another N atom. Trigonal-pyramidal copper environment comprises of two nitrogen atoms from different ligand units, CC-bond and oxygen atom at the apical position. The bridging function of both Cu⁺ cations and 2-all-bta molecules results in the formation of infinite chains. High affinity of BF₄^{鈭?/sup> anion to the H₂O leads to a formation of compound III including water molecule. It crystallizes in an orthorhombic Pbca space group, a聽=聽13.502(8)聽脜 b聽=聽11.299(5)聽脜 c聽=聽16.124(8)聽脜, V聽=聽2460(2)聽脜3, Z聽=聽8. The ligand moiety plays the same as in I and II chelate-bridging function, but Cu+, being also bonded to CC group and to two N atoms, is connected with the disordered BF₄鈭?/sup> anion through the water bridge. In the crystal structure IV the metal ion possesses mixed-isomer surrounding, being bound to N-atom and CC-bond of 2-all-bta molecule, N-atom of 1-all-bta-moiety and O(ClO₄鈭?/sup>) atom at apical position. IR spectra confirm rather effective Cu-(CC) bonding.}