http://repository.iitr.ac.in/handle/123456789/20730| Title: | Observation of Carbodicarbene Ligand Redox Noninnocence in Highly Oxidized Iron Complexes |
| Authors: | Chan S.-C. Gupta, Puneet Engelmann X. Ang Z.Z. Ganguly R. Bill E. Ray K. Ye S. England J. |
| Published in: | Angewandte Chemie - International Edition |
| 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 |
| Citation: | Angewandte Chemie - International Edition, 57(48): 15717-15722 |
| URI: | https://doi.org/10.1002/anie.201809158 http://repository.iitr.ac.in/handle/123456789/20730 |
| Issue Date: | 2018 |
| Publisher: | Wiley-VCH Verlag |
| Keywords: | carbodicarbenes cationic ligands iron radical ions redox noninnocence |
| ISSN: | 14337851 |
| Author Scopus IDs: | 36697633900 57215231630 57190024704 57212246724 55675224139 35508351700 7203056066 8346771900 9239275100 |
| Author Affiliations: | Chan, S.-C., Division of Chemistry and Biological Chemistry, School of Physical & Mathematical Sciences, Nanyang Technological University, 21 Nanyang Link, Singapore, 637371, Singapore Gupta, P., Max-Plank-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, Mülheim an der Ruhr, 45470, Germany Engelmann, X., Department of Chemistry, Humboldt-Universität zu Berlin, Brook-Taylor-Straße 2, Berlin, 12489, Germany Ang, Z.Z., Division of Chemistry and Biological Chemistry, School of Physical & Mathematical Sciences, Nanyang Technological University, 21 Nanyang Link, Singapore, 637371, Singapore Ganguly, R., Division of Chemistry and Biological Chemistry, School of Physical & Mathematical Sciences, Nanyang Technological University, 21 Nanyang Link, Singapore, 637371, Singapore Bill, E., Max-Plank-Institut für Chemische Energie Konversion, Stiftstraße 34–36, Mülheim an der Ruhr, 45470, Germany Ray, K., Department of Chemistry, Humboldt-Universität zu Berlin, Brook-Taylor-Straße 2, Berlin, 12489, Germany Ye, S., Max-Plank-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, Mülheim an der Ruhr, 45470, Germany England, J., Division of Chemistry and Biological Chemistry, School of Physical & Mathematical Sciences, Nanyang Technological University, 21 Nanyang Link, Singapore, 637371, Singapore |
| Funding Details: | J.E. is grateful to NTU for funding (M4081442). P.G., E.B. and S.Y. gratefully acknowledge the financial support of the Max-Planck Society. K.R. thanks the DFG for a Heisenberg Professorship. Deutsche Forschungsgemeinschaft, DFG; Max-Planck-Gesellschaft, MPG; Nantong University, NTU: M4081442 |
| Corresponding Author: | Ye, S.; Max-Plank-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, Germany; email: shengfa.ye@kofo.mpg.de |
| Appears in Collections: | Journal Publications [CY] |
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