Thomas Kolle E, Beavers Christine M, Gagnon Kevin J, Ghosh Abhik
Department of Chemistry and Center for Theoretical & Computational Chemistry UiT-The Arctic University of Norway 9037 Tromsø Norway.
Advanced Light Source Lawrence Berkeley National Laboratory Berkeley CA 94720-8229 USA.
ChemistryOpen. 2017 May 26;6(3):402-409. doi: 10.1002/open.201700035. eCollection 2017 Jun.
Presented herein is a study of the acid-induced demetalation of two sterically hindered copper corroles, Cu β-octabromo--triphenylcorrole (Cu[BrTPC]) and β-octakis(trifluoromethyl)--tris(-methoxyphenyl)corrole (Cu[(CF)TOMePC]). Unlike reductive demetalation, which affords the free-base β-octabromocorrole, demetalation of Cu[BrTPC] under non- reductive conditions (CHCl/HSO) resulted in moderate yields of free-base 5- and 10-hydroxy isocorroles. The isomeric free bases could be complexed to Co and Ni, affording stable complexes. Only reductive demetalation was found to work for Cu[(CF)TOMePC], affording a highly saddled, hydrated corrole, H[5-OH,10-H-(CF)TOMePC], where the elements of water had added across C and C. Interaction of this novel free base with Co resulted in Co[-10-H-[CF)TOMePC], a Co 10-hydro isocorrole. The new metal complexes were all characterized by single-crystal X-ray diffraction analysis and, despite their sterically hindered nature, were found to exhibit almost perfectly planar isocorrole cores.
本文介绍了对两种空间位阻较大的铜卟啉（Cu β-八溴-三苯基卟啉（Cu[BrTPC]）和β-八（三氟甲基）-三（甲氧基苯基）卟啉（Cu[(CF)TOMePC]））的酸诱导脱金属反应的研究。与还原脱金属反应不同，还原脱金属反应可得到游离碱β-八溴卟啉，而在非还原条件下（CHCl/HSO）对Cu[BrTPC]进行脱金属反应，可得到中等产率的游离碱5-和10-羟基异卟啉。这些异构游离碱可与Co和Ni络合，形成稳定的络合物。仅发现还原脱金属反应适用于Cu[(CF)TOMePC]，得到一种高度鞍形的水合卟啉，H[5-OH,10-H-(CF)TOMePC]，其中水的成分已加成到C和C上。这种新型游离碱与Co的相互作用产生了Co[-10-H-[CF)TOMePC]，一种Co 10-氢异卟啉。所有新的金属络合物均通过单晶X射线衍射分析进行了表征，尽管它们具有空间位阻性质，但发现其异卟啉核心几乎呈完美平面。
