Observation of Carbodicarbene Ligand Redox Noninnocence in Highly Oxidized Iron Complexes

Chan, S.-C., Gupta, P., Engelmann, X. , Ang, Z.Z., Ganguly, R., Bill, E., Ray, K., Ye, S. and England, Jason (2018) Observation of Carbodicarbene Ligand Redox Noninnocence in Highly Oxidized Iron Complexes. Angewandte Chemie - International Edition, 57 (48). pp. 15717-15722. ISSN 1433-7851

Full content URL: https://doi.org/10.1002/anie.201809158

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Observation of Carbodicarbene Ligand Redox Noninnocence in Highly Oxidized Iron Complexes
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Abstract

To probe the possibility that carbodicarbenes (CDCs) are redox active ligands, all four members of the redox series [Fe(1)2]n+ (n = 2 - 5) were synthesized, where 1 is a neutral tridentate CDC. Through a combination of spectroscopy and DFT calculations, the electronic structure of the pentacation is shown to be [FeIII(1.+)2]5+ (S = (Formula presented.)). That of [Fe(1)2]4+ is more ambiguous, but it has significant contributions from the open-shell singlet [FeIII(1)(1.+)]4+ (S=0). The observed spin states derive from antiferromagnetic coupling of their constituent low-spin iron(III) centres and cation radical ligands. This marks the first time redox activity has been observed for carbones and expands the diverse chemical behaviour known for these ligands. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Keywords:Electronic structure, Iron, Ligands, Redox reactions, Antiferromagnetic coupling, carbodicarbenes, Cation-radicals, DFT calculation, Radical ions, Redox activity, Redox non innocences, Redox-active ligand, Iron compounds
Subjects:F Physical Sciences > F120 Inorganic Chemistry
F Physical Sciences > F161 Organometallic Chemistry
Divisions:College of Science > School of Chemistry
ID Code:51898
Deposited On:04 Oct 2022 08:38

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