A macrocyclic ligand 5,14-dihydro-6,15-dimethyl-8,17-diphenyldibenzo-[b,i] [1,4,8,11]tetraazacyclotetradecine and its nickel(II) complex: Syntheses, reaction mechanism and structures

Xuan Shen, Lu Sun, Bo Kun Jiang, Xin Wang, Akio Nakashima, Naoki Miyamoto, Kazunori Sakata, Yan Xu, Dun Ru Zhu

科研成果: 期刊稿件文章同行评审

3 引用 (Scopus)

摘要

The template reaction of o-phenylenediamine, 1-benzoylacetone and nickelous acetate tetrahydrate results in two structure isomers, 6,17-dimethyl-8,15- diphenyldibenzo[b,i][1,4,8,11]tetraazacyclotetradecinatonickel (II) (2) and 6,15-dimethyl-8,17-diphenyldibenzo[b,i][1,4,8,11] tetraazacyclotetradecinatonickel (II) (4). However, the latter has been neglected in the previous research because of its low yield in the template reaction. The mechanism of this template reaction is discussed. Though the steric hindrance between the phenyl ring and the benzo ring in 2 is greater than that in 4, the intermediate of the former shows better structural stability than that of the latter, leading to obviously higher final yield of 2 compared with that of 4. n-Butyl alcohol is used artfully to separate the crude product of the template reaction into almost pure 2 and a mixture of 2 and 4 in a mole ratio of 1:5. The free base of 2, 5,14-dihydro-6,17-dimethyl-8,15- diphenyldibenzo[b,i][1,4,8,11]tetraazacyclotetradecine (1), can be synthesized by demetalization of 2 with gaseous HCl. The same treatment to the mixture of 2 and 4 in a mole ratio of 1:5 leads to the free base of 4, 5,14-dihydro-6,15- dimethyl-8,17-diphenyldibenzo[b,i][1,4,8,11]tetraazacyclotetradecine (3). The neglected macrocyclic compounds 3 and 4 have been characterized unambiguously and their single-crystal structures have also been determined by X-ray diffraction analysis for the first time.

源语言英语
页(从-至)1555-1560
页数6
期刊Inorganic Chemistry Communications
14
10
DOI
出版状态已出版 - 10月 2011

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