Formation of Stable NiIII N-Confused Porphyrins Aided by a 3-Ethoxy Group.

Huowang He, Zongren Ye, Daiki Shimizu, Idrees Sumra, Yihuan Zhang, Zhengyu Liang, Yingyu Zeng, Ling Xu, Atsuhiro Osuka, Zhuofeng Ke, Hua-Wei Jiang

Chemistry (Weinheim an der Bergstrasse, Germany) 2022 Jan 03

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We report the synthesis, characterization, and reactivities of two stable NiIII N-confused porphyrin (NCP) complexes. Metalation of 3-OEt NCP 1 with NiCl2 ⋅ 6H2 O in CHCl3 /EtOH gave 3-OEt NiII NCP 3 initially, which was easily oxidized in air to form the NiIII complex of NCP inner C-oxide 4. Bis-ethoxy-modified NiIII complex 5 was synthesized by oxidation of 3 with PIFA in ethanol and CHCl3 . The structures of 4 and 5 were determined by single-crystal X-ray diffraction analysis. An unusually long NiIII -C bond (2.170(9) Å) was observed in 4. The g-factor (g>2.1) observed in the EPR spectra of 4 and 5 further confirmed that they are paramagnetic NiIII complexes. Comparative experiments showed that the 3-ethoxy group plays an important role in the formation of 4 and 5. Reduction of 4 and 5 with NaBH4 regenerated complex 3. © 2021 Wiley-VCH GmbH.

Citation

Huowang He, Zongren Ye, Daiki Shimizu, Idrees Sumra, Yihuan Zhang, Zhengyu Liang, Yingyu Zeng, Ling Xu, Atsuhiro Osuka, Zhuofeng Ke, Hua-Wei Jiang. Formation of Stable NiIII N-Confused Porphyrins Aided by a 3-Ethoxy Group. Chemistry (Weinheim an der Bergstrasse, Germany). 2022 Jan 03;28(1):e202103272