Institute for Inorganic and Analytical Chemistry, TU Braunschweig, Hagenring 30, 38106, Braunschweig, Germany.
Angew Chem Int Ed Engl. 2017 Aug 7;56(33):9967-9970. doi: 10.1002/anie.201705551. Epub 2017 Jul 17.
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 N 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.
10-杂异卟啉配合物在大环的 10 位上具有氧、硫和硒，以及二价镍、铜和钯离子，这些配合物已被制备并进行了研究。重点是研究腔大小与卟啉型大环中离子半径的尺寸适应和匹配机制。一整套单晶 X 射线分析数据表明，除了一种情况外，环缩合的四吡咯的 N 键合位都大于在不发生变形的情况下结合金属离子所需的大小。通过 M-N 键长延长 2.5-3.2%的面内尺寸适应以及对那些具有更严重尺寸不匹配的化合物的大环的明显的面外起皱是有效的。以前曾排除了卟啉的这种起皱，但显然是适应小中心离子的最有效机制。
