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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Metallacrowns of Ni(ii) with α-aminohydroxamic acids in aqueous solution: Beyond a 12-MC-4, an unexpected (vacant?) 15-MC-5
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Metallacrowns of Ni(ii) with α-aminohydroxamic acids in aqueous solution: Beyond a 12-MC-4, an unexpected (vacant?) 15-MC-5

机译：水溶液中的Ni（ii）与α-氨基异羟肟酸的金属漆：超出12-MC-4的范围，出乎意料的（空的？）15-MC-5

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摘要

Growing attention has been devoted in the recent years to a class of metallamacrocycles known as metallacrowns (MCs). They are structural analogues of crown ethers where the methylene bridges have been substituted by coordinative bonds formed by a transition metal ion ("ring" metal) and a nitrogen atom. The cavity of the metallacrown can accommodate an additional metal ion ("core" metal) either identical or different from the ring metal, thus forming a homo- or hetero-metallic MC. The most studied ring metal ion is certainly Cu2+ and the aminohydroxamic acids have proved to be very suitable ligands to form MCs. The behavioural analogies between Cu 2+ and Ni2+ in forming complexes, along with recent literature data in the solid state, prompted us to investigate the possible MC formation between Ni2+ and both (S)-α-alaninehydroxamic acid and (S)-valinehydroxamic acid, in aqueous solution. Two metallacrowns, a 12-MC-4 and an unexpected 15-MC-5 have been detected by potentiometry and confirmed by ESI-MS results. Their structures are discussed on the basis of potentiometric, calorimetric, spectroscopic data and DFT calculations. The existence of a vacant 15-MC-5 species in solution can be put forward for the first time, making the present metal/ligand systems very interesting for their potential applications in cation recognition and separation. Finally, the crystal structure of the binary complex K[NiL2H-1]·5/3 H2O of (S)-α-alaninehydroxamic acid (LH) is also reported.
机译：近年来，人们越来越关注一类称为金属漆row（MC）的金属lamcrocrocycles。它们是冠醚的结构类似物，其中亚甲基桥已被过渡金属离子（“环”金属）和氮原子形成的配位键取代。金属胎冠的腔可以容纳与环金属相同或不同的另外的金属离子（“芯”金属），从而形成均金属或异金属MC。研究最多的环金属离子当然是Cu2 +，并且氨基异羟肟酸已被证明是非常适合形成MC的配体。 Cu 2+和Ni2 +在形成络合物中的行为相似性，以及最近的固态文献资料，促使我们研究Ni2 +与（S）-α-丙氨酸异羟肟酸和（S）-缬氨酸异羟肟酸之间可能的MC形成，在水溶液中。通过电位计检测到两个金属缺口，即12-MC-4和意外的15-MC-5，并通过ESI-MS结果进行了确认。根据电位，量热，光谱数据和DFT计算讨论了它们的结构。可以首次提出溶液中空的15-MC-5物种的存在，这使得本金属/配体系统因其在阳离子识别和分离中的潜在应用而引起人们的极大兴趣。最后，还报道了（S）-α-丙氨酸异羟肟酸（LH）的二元配合物K [NiL2H-1]·5/3 H2O的晶体结构。

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