Observation of Carbodicarbene Ligand Redox Noninnocence in Highly Oxidized Iron Complexes
Dr. Siu-Chung Chan
Division of Chemistry and Biological Chemistry, School of Physical & Mathematical Sciences, Nanyang Technological University, 21 Nanyang Link, Singapore, 637371 Singapore
These authors contributed equally to this work.
Search for more papers by this authorDr. Puneet Gupta
Max-Plank-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, 45470 Mülheim an der Ruhr, Germany
These authors contributed equally to this work.
Search for more papers by this authorXenia Engelmann
Department of Chemistry, Humboldt-Universität zu Berlin, Brook-Taylor-Straße 2, 12489 Berlin, Germany
Search for more papers by this authorZhi Zhong Ang
Division of Chemistry and Biological Chemistry, School of Physical & Mathematical Sciences, Nanyang Technological University, 21 Nanyang Link, Singapore, 637371 Singapore
Search for more papers by this authorDr. Rakesh Ganguly
Division of Chemistry and Biological Chemistry, School of Physical & Mathematical Sciences, Nanyang Technological University, 21 Nanyang Link, Singapore, 637371 Singapore
Search for more papers by this authorDr. Eckhard Bill
Max-Plank-Institut für Chemische Energie Konversion, Stiftstraße 34–36, 45470 Mülheim an der Ruhr, Germany
Search for more papers by this authorProf. Dr. Kallol Ray
Department of Chemistry, Humboldt-Universität zu Berlin, Brook-Taylor-Straße 2, 12489 Berlin, Germany
Search for more papers by this authorCorresponding Author
Dr. Shengfa Ye
Max-Plank-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, 45470 Mülheim an der Ruhr, Germany
Search for more papers by this authorCorresponding Author
Assist. Prof. Jason England
Division of Chemistry and Biological Chemistry, School of Physical & Mathematical Sciences, Nanyang Technological University, 21 Nanyang Link, Singapore, 637371 Singapore
Search for more papers by this authorDr. Siu-Chung Chan
Division of Chemistry and Biological Chemistry, School of Physical & Mathematical Sciences, Nanyang Technological University, 21 Nanyang Link, Singapore, 637371 Singapore
These authors contributed equally to this work.
Search for more papers by this authorDr. Puneet Gupta
Max-Plank-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, 45470 Mülheim an der Ruhr, Germany
These authors contributed equally to this work.
Search for more papers by this authorXenia Engelmann
Department of Chemistry, Humboldt-Universität zu Berlin, Brook-Taylor-Straße 2, 12489 Berlin, Germany
Search for more papers by this authorZhi Zhong Ang
Division of Chemistry and Biological Chemistry, School of Physical & Mathematical Sciences, Nanyang Technological University, 21 Nanyang Link, Singapore, 637371 Singapore
Search for more papers by this authorDr. Rakesh Ganguly
Division of Chemistry and Biological Chemistry, School of Physical & Mathematical Sciences, Nanyang Technological University, 21 Nanyang Link, Singapore, 637371 Singapore
Search for more papers by this authorDr. Eckhard Bill
Max-Plank-Institut für Chemische Energie Konversion, Stiftstraße 34–36, 45470 Mülheim an der Ruhr, Germany
Search for more papers by this authorProf. Dr. Kallol Ray
Department of Chemistry, Humboldt-Universität zu Berlin, Brook-Taylor-Straße 2, 12489 Berlin, Germany
Search for more papers by this authorCorresponding Author
Dr. Shengfa Ye
Max-Plank-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, 45470 Mülheim an der Ruhr, Germany
Search for more papers by this authorCorresponding Author
Assist. Prof. Jason England
Division of Chemistry and Biological Chemistry, School of Physical & Mathematical Sciences, Nanyang Technological University, 21 Nanyang Link, Singapore, 637371 Singapore
Search for more papers by this authorGraphical Abstract
Carbones contain C atoms possessing two lone pairs of electrons. Thus, along with σ-coordination to a metal ion, they have a further pair of electrons, rendering them capable of π-donation or geminal coordination to a second metal. Via formation of a [Fe(1)2]n+ (n=2–5) redox series, where 1 is a tridentate carbodicarbene ligand, it is shown that this second pair of electrons also allows them to be redox-active.
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=
). 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.
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