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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Preparation and characterization of asymmetric alpha-alkoxy dipyrrin ligands and their metal complexes
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Preparation and characterization of asymmetric alpha-alkoxy dipyrrin ligands and their metal complexes

机译：不对称α-烷氧基二吡啶配体及其金属配合物的制备与表征

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摘要

Asymmetric alpha-substituted dipyrrins have been synthesized and characterized. The compounds were formed by a metal mediated reaction involving a single alkoxy group substituted into the a-position of an alpha, beta-unsubstituted dipyrrin. An alpha-methoxy dipyrrin, 5-(4-cyanophenyl)-1-methoxydipyrrin (alpha-OMe-4-cydpm), was prepared from 5-(4-cyanophenyl)-4,6-dipyrromethane. Methoxy, ethoxy, and propoxy derivatives (alpha-OMe-4-mecdpm, alpha-OEt-4-mecdpm, alpha-OPr-4-mecdpm) of 5-(4-methoxycarbonylphenyl)4,6-dipyrromethane have also been prepared. A homoleptic, bis(1-methoxy)dipyrrinato zinc(II) complex, [Zn(alpha-OMe-4-mecdpm)(2)], has been synthesized, as has a heteroleptic cobalt(III) complex with one alpha-OMe-4-cydpm ligand and two unsubstituted 5-(4-cyanophenyl) dipyrrin (4-cydpm) ligands ([Co(alpha-OMe-4-cydpm)(4-cydpm)(2)]). The rotational barrier of the meso-aryl substituent of[Zn(alpha-OMe-4-mecdpm)(2)] was found to be 17.3 kcal mol(-1) by variable-temperature NMR spectroscopy. The compounds alpha-OMe-4-cydpm and [Zn(alpha-OMe-4-mecdpm)(2)] have also been characterized by X-ray diffraction. The formation of the new dipyrrin derivatives is shown to be general and can be performed on dipyrrins with various meso-aryl substitutents, with a variety of alcohols, and can be promoted by several metal salts.
机译：已经合成和表征了不对称的α-取代的二吡啶。这些化合物是通过金属介导的反应形成的，该反应涉及一个被单个取代的烷氧基取代成一个α，β-未取代的双吡啶。由5-（4-氰基苯基）-4，6-二吡咯甲烷制备α-甲氧基二吡啶，5-（4-氰基苯基）-1-甲氧基二吡啶（α-OMe-4-cydpm）。还制备了5-（4-甲氧基羰基苯基）4，6-二吡咯甲烷的甲氧基，乙氧基和丙氧基衍生物（α-OMe-4-mecdpm，α-OEt-4-mecdpm，α-OPr-4-mecdpm）。合成了一种均衡的双（1-甲氧基）双吡啶并锌（II）配合物[Zn（alpha-OMe-4-mecdpm）（2）]，以及一种具有一个alpha-OMe的杂配钴（III）配合物。 -4-cydpm配体和两个未取代的5-（4-氰基苯基）二吡啶（4-cydpm）配体（[Co（alpha-OMe-4-cydpm）（4-cydpm）（2）]）。通过变温NMR光谱发现[Zn（α-OMe-4-mecdpm）（2）]的内-芳基取代基的旋转势垒为17.3 kcal mol（-1）。化合物α-OMe-4-cydpm和[Zn（α-OMe-4-mecdpm）（2）]也已通过X射线衍射表征。已显示出新的二吡啶衍生物的形成是普遍的，并且可以在具有各种内消旋芳基取代基，多种醇的二吡啶上进行，并且可以由几种金属盐促进。

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