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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Heavier alkali metal complexes of 2-phenylamidopyridine: An X-ray crystallographic and theoretical study of a structurally diverse series of crown ether adducts
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Heavier alkali metal complexes of 2-phenylamidopyridine: An X-ray crystallographic and theoretical study of a structurally diverse series of crown ether adducts

机译：2-苯基酰胺基吡啶的较重碱金属配合物：一系列结构多样的冠醚加合物的X射线晶体学和理论研究

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摘要

Complexes of the anion of the secondary amine 2-phenylaminopyridine (LH) with the heavier alkali metals Na-Cs have been prepared in the presence of various macrocyclic polyether crowns [12-crown-4 (12C4), 15-crown-5 (15C5), and 18-crown-6 (18C6)], which coordinate to the metal ions in all cases. Depending on the combination of alkali metal and crown, the products include separated ion pairs [(crown)(2)M]L-+(-) (12C4/Na, 15C5/K, 15C5/Rb, 15C5/Cs) and contact-ion-pair neutral molecules [(crown)ML] (15C5/Na, 18C6/Na, 18C6/K, 18C6/Rb) in which L- acts as a bidentate ligand. [{(12C4)KL}(2)] is a dimer in which the amido and pyridine N atoms of two ligands bridge the metal ions, while [{(18C6)KL2K}(infinity)] is a chain polymer with crown O and pyridyl N atoms acting as bridges in corner-sharing KOKN four-membered rings and may be regarded as a potassium potassate complex. [{(18C6)Cs2L2}(infinity)] is also polymeric, with a basic arrangement like that of [{(12C4)KL}(2)], but with each 18C6 ligand mu-kappa(6) : kappa(6) to two metal centres, generating the polymer. Although most of the [(crown)(2)M](+) sandwich cations have essentially parallel crown ligands, [(12C4)(2)Rb](+) is markedly bent, both in the complex incorporating THF as an additional ligand and in the THF-free complex, where two of these cations form a centrosymmetric dimer through two bridging oxygen atoms; DFT calculations indicate that the bending is inherent, thus enabling the coordination by an extra oxygen atom rather than being a consequence of this coordination. Attempts to isolate the caesium 12C4 derivative were unsuccessful. The compounds have been characterized by NMR spectroscopy, CHN microanalysis and, in most cases, X-ray crystallography.
机译：仲胺2-苯基氨基吡啶（LH）的阴离子与较重的碱金属Na-Cs的配合物是在各种大环聚醚冠[12-cro-4（12C4），15-cro-5（15C5） ）和18-crown-6（18C6）]，它们在所有情况下均与金属离子配位。根据碱金属和冠的组合，产品包括分离的离子对[（冠）（2）M] L-+（-）（12C4 / Na，15C5 / K，15C5 / Rb，15C5 / Cs）和接触-离子对中性分子[（crown）ML]（15C5 / Na，18C6 / Na，18C6 / K，18C6 / Rb），其中L-作为双齿配体。 [{（12C4）KL}（2）]是一种二聚体，其中两个配体的酰胺和吡啶N原子桥接金属离子，而[{（18C6）KL2K}（Infinity）]是具有冠O和吡啶N原子充当角共享KOKN四元环中的桥，并可能被认为是钾钾盐络合物。 [{（18C6）Cs2L2}（infinity）]也是聚合的，其基本排列类似于[{（12C4）KL}（2）]，但每个18C6配体均是mu-kappa（6）：kappa（6）到两个金属中心，生成聚合物。尽管大多数[（crown）（2）M]（+）夹心阳离子都具有基本平行的冠状配体，但[（12C4）（2）Rb]（+）明显弯曲，在包含THF作为附加配体的配合物中在无THF配合物中，其中两个阳离子通过两个桥接氧原子形成一个中心对称的二聚体; DFT计算表明，弯曲是固有的，因此可以通过额外的氧原子进行配位，而不是这种配位的结果。分离铯12C4衍生物的尝试未成功。该化合物已通过NMR光谱，CHN微量分析以及大多数情况下的X射线晶体学进行了表征。

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