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Heterocorrole Conformations: Little Saddling, Much Ruffling
Angewandte Chemie International Edition ( IF 16.1 ) Pub Date : 2017-07-17 06:50:56 , DOI: 10.1002/anie.201705551
Jörn Rösner 1 , Birte Cordes 1 , Stefanie Bahnmüller 1 , Gabor Homolya 1 , Dimitri Sakow 1 , Peter Schweyen 1 , Richard Wicht 1 , Martin Bröring 1
Affiliation  

10-Heterocorrole complexes with oxygen, sulfur, and selenium at position 10 of the macrocycle and with the divalent ions of nickel, copper, and palladium were prepared and investigated. The focus was set on the size adaptation and matching mechanisms of cavity size versus ionic radius in corrole-type macrocycles. A full set of single-crystal X-ray analytical data revealed that in all but one case the N4 binding site of the ring-contracted tetrapyrrole was larger than necessary to bind the metal ion without deformation. In-plane size adaptation through M−N bond-length elongation by 2.5–3.2 % was effective, as well as pronounced out-of-plane ruffling of the macrocycle for those compounds with a more severe size mismatch. Such ruffling had been excluded for corroles previously, but is apparently the most efficient mechanism to adapt to small central ions.

中文翻译:

异戊二烯构象:小鞍形,多波纹形

制备并研究了在大环的10位与氧,硫和硒以及镍,铜和钯的二价离子形成的10-杂环化合物。重点放在腐蚀型大环化合物中腔尺寸与离子半径的尺寸适应和匹配机制上。全套的单晶X射线分析数据表明,除一种情况外,N 4环缩合的四吡咯的结合位点大于结合金属离子而不变形所需的位点。通过M–N键长延长2.5–3.2%进行的面内尺寸匹配非常有效,并且对于那些具有更严重的尺寸失配的化合物,大环的面外波纹更有效。以前,这些杂波已排除在外,但显然是适应小中心离子的最有效机制。
更新日期:2017-07-17
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