Towards Norcorrin: Hydrogenation Chemistry and the Heterodimerization of Nickel(II) Norcorrole

Bin Liu; Xiaofang Li; Marcin Stępień; Piotr J Chmielewski

doi:10.1002/chem.201500736

Towards Norcorrin: Hydrogenation Chemistry and the Heterodimerization of Nickel(II) Norcorrole

Chemistry. 2015 May 18;21(21):7790-7. doi: 10.1002/chem.201500736. Epub 2015 Apr 20.

Authors

Bin Liu¹, Xiaofang Li, Marcin Stępień, Piotr J Chmielewski

Affiliation

¹ Key Laboratory of Theoretical Organic Chemistry and Functional Molecules, Ministry of Education, School of Chemistry and Chemical Engineering, Hunan University of Science and Technology, Xiangtan, Hunan 411201 (P. R. China).

PMID: 25899073
DOI: 10.1002/chem.201500736

Abstract

5,14-Dimesitylnorcorrolatonickel(II) was hydrogenated under mild conditions (room temperature, 1 atm H2 , THF solution, 5 min.) in the presence of Raney nickel to yield nonaromatic derivatives that were isolated and characterized by NMR spectroscopy, UV/Vis spectrophotometry, HRMS, cyclic voltammetry, and X-ray diffraction analysis. The major hydrogenation product, 1,2,3,7,8,9-hexahydronorcorrolatonickel(II), underwent dimerization in the presence of p-chloranil to give a nonsymmetrically linked 2,3'-bis(norcorrole) system that can adopt eight different oxidation states over a redox potential window of 3 V and has a HOMO-LUMO gap of 0.92 V.

Keywords: dimerization; hydrogenation; nickel; porphyrinoids; reduction.