NiII and CuII Complexes of 5-Oxa-, 5-Sulfa-, 5-Selena-, and 5-Telluracorroles

作者：Xiaoyan Wan, Yutao Rao, Ling Xu, Bangshao Yin, Mingbo Zhou, Daiki Shimizu, Atsuhiro Osuka, Jianxin Song · 发表于：Organic Letters · 年份：2025 · DOI：10.1021/acs.orglett.5c03160 · 被引用次数：3 · 研究领域：Porphyrin and Phthalocyanine Chemistry、Photochemistry and Electron Transfer Studies、Magnetism in coordination complexes

Cyclization of α,α’ -dibromo tetrapyrrolic Ni II complex 4Ni with K 2 S, Na 2 Se, and Na 2 Te gave Ni II 5-sulfacorrole, Ni II 5-selenacorrole, and Ni II 5-telluracorrole, respectively, as the first example of 5-heterocorrole. The corresponding Cu II 5-heterocorroles were similarly synthesized from Cu II complex 4Cu, while Ni II 5-oxacorrole was synthesized by reaction of 4Ni with Ni(cod) 2 and 2,2’-bipyridine and subsequent oxygen-insertion reaction of molecular oxygen, and Cu II 5-oxacorrole was obtained from reaction of 4Cu with Cu I thiophene-2-carboxylate (CuTC) and tetrabutylammonium hydroxide. Moderate aromatic characters of the Ni II 5-heterocorroles are evinced by the 1 H NMR chemical shifts, the absorption spectra, and DFT calculations. ESR measurement and simulation studies on the Cu II 5-heterocorroles revealed that spins are largely centered on the Cu II but a reduced spin density at the Cu II is indicated for the Cu II 5-telluracorrole.