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      Metal Complexes of Indigo and of Some Related Ligands

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      Zeitschrift für anorganische und allgemeine Chemie
      Wiley

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          Ludwig Mond Lecture. High-carat gold compounds

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            Manifestations of Noninnocent Ligand Behavior

            The potential of redox-active ligands to behave "noninnocently" in transition-metal coordination compounds is reflected with respect to various aspects and situations. These include the question of establishing "correct" oxidation states, the identification and characterization of differently charged radical ligands, the listing of structural and other consequences of ligand redox reactions, and the distinction between barrierless delocalized "resonance" cases M(n)/L(n) ↔ M(n+1)L(n-1) versus separated valence tautomer equilibrium situations M(n)/L(n) ⇌ M(n+1)L(n-1). Further ambivalence arises for dinuclear systems with radical bridge M(n)(μ-L(•))M(n) versus mixed-valent alternatives M(n+1)(μ-L(-))M(n), for noninnocent ligand-bridged coordination compounds of higher nuclearity such as (μ(3)-L)M(3), (μ(4)-L)M(4), (μ-L)(4)M(4), or coordination polymers. Conversely, the presence of more than one noninnocently behaving ligand at a single transition-metal site in situations such as L(n)-M-L(n-1) or L(•)-M-L(•) may give rise to corresponding ligand-to-ligand interaction phenomena (charge transfer, electron hopping, and spin-spin coupling) and to redox-induced electron transfer with counterintuitive oxidation-state changes. The relationships of noninnocent ligand behavior with excited-state descriptions and perspectives regarding material properties and single-electron or multielectron reactivity are also illustrated briefly.
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              Indigoid Photoswitches: Visible Light Responsive Molecular Tools

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                Author and article information

                Journal
                Zeitschrift für anorganische und allgemeine Chemie
                Z. Anorg. Allg. Chem.
                Wiley
                0044-2313
                1521-3749
                February 28 2020
                February 18 2020
                February 28 2020
                : 646
                : 4
                : 248-255
                Affiliations
                [1 ]Department Chemie Ludwig‐Maximilians‐Universität München Butenandtstr. 5‐13 (D) 81377 München Germany
                Article
                10.1002/zaac.201900363
                9b613013-4312-41e7-a7d7-a58471ac27a5
                © 2020

                http://creativecommons.org/licenses/by/4.0/

                http://doi.wiley.com/10.1002/tdm_license_1.1

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