Redox-Active Ligand-Induced Homolytic Bond Activation

Coordination of the novel redox‐active phosphine‐appended aminophenol pincer ligand (PNOH2) to PdII generates a paramagnetic complex with a persistent ligand‐centered radical. The complex undergoes fully reversible single‐electron oxidation and reduction. Homolytic bond activation of diphenyldisulfi...

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Bibliographic Details
Published in:	Angewandte Chemie International Edition Vol. 54; no. 5; pp. 1516 - 1520
Main Authors:	Broere, Daniël L. J., Metz, Lotte L., de Bruin, Bas, Reek, Joost N. H., Siegler, Maxime A., van der Vlugt, Jarl Ivar
Format:	Journal Article
Language:	English
Published:	Weinheim WILEY-VCH Verlag 26.01.2015 WILEY‐VCH Verlag Wiley Wiley Subscription Services, Inc
Edition:	International ed. in English
Subjects:	Activation bond activation Bonding Chemistry Chemistry, Multidisciplinary Coordination Complexes - chemical synthesis Coordination Complexes - chemistry Crystallography, X-Ray Disulfides - chemistry Electron Spin Resonance Spectroscopy Electron Transport Ligands mixed valency Molecular Conformation Oxidation-Reduction Palladium Palladium - chemistry phosphane ligands Phosphines Physical Sciences Radicals redox-active ligands Reduction Science & Technology Strategy mixed valency CATALYSIS TRANSITION-METAL-COMPLEXES bond activation REACTIVITY IRON OXIDATIVE ADDITION ELECTRONIC-STRUCTURES phosphane ligands MONONUCLEAR redox-active ligands RUTHENIUM COMPLEXES palladium THIYL RADICALS PALLADIUM(II)
ISSN:	1433-7851, 1521-3773, 1521-3773
Online Access:	Get full text
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Summary:	Coordination of the novel redox‐active phosphine‐appended aminophenol pincer ligand (PNOH2) to PdII generates a paramagnetic complex with a persistent ligand‐centered radical. The complex undergoes fully reversible single‐electron oxidation and reduction. Homolytic bond activation of diphenyldisulfide by the single‐electron reduced species leads to a ligand‐based mixed‐valent dinuclear palladium complex with a single bridging thiolate ligand. Mechanistic investigations support an unprecedented intramolecular ligand‐to‐disulfide single‐electron transfer process to induce homolytic SS cleavage, thereby releasing a thiyl (sulfanyl) radical. This could be a new strategy for small‐molecule bond activation. PNO duet: The redox‐active pincer ligand PNO, which has a flanking phosphine group, can coordinate to PdII in various oxidation states. One‐electron reduction from paramagnetic [PdCl(PNO)] generates a competent reagent for the homolytic bond activation of disulfides through ligand‐to‐substrate single‐electron transfer. The resulting dinuclear Pd species, which has a monothiolate bridgehead, shows well‐defined ligand mixed valency in the solid state.
Bibliography:	ark:/67375/WNG-DQR8F39D-1 istex:76E48C31616FAC976DF667C04D71C4A49A3C82F7 European Research Council - No. 279097 Research funded by the European Research Council (ERC Starting Grant 279097 to J.I.v.d.V.). We thank Ed Zuidinga for assistance with ESI-MS measurements. ArticleID:ANIE201410048 Research funded by the European Research Council (ERC Starting Grant 279097 to J.I.v.d.V.). We thank Ed Zuidinga for assistance with ESI‐MS measurements. ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 14 content type line 23
ISSN:	1433-7851 1521-3773 1521-3773
DOI:	10.1002/anie.201410048