Metalloradical Reactivity of RuI and Ru0 Stabilized by an Indole-Based Tripodal Tetraphosphine Ligand

Fenna F van de Watering; Jarl Ivar van der Vlugt; Wojciech I Dzik; Bas de Bruin; Joost N H Reek

doi:10.1002/chem.201702727

Metalloradical Reactivity of Ru^I and Ru⁰ Stabilized by an Indole-Based Tripodal Tetraphosphine Ligand

Chemistry. 2017 Sep 18;23(52):12709-12713. doi: 10.1002/chem.201702727. Epub 2017 Aug 30.

Authors

Fenna F van de Watering¹, Jarl Ivar van der Vlugt¹, Wojciech I Dzik¹, Bas de Bruin¹, Joost N H Reek¹

Affiliation

¹ Homogeneous, Supramolecular and Bio-Inspired Catalysis, Van't Hoff Institute for Molecular Sciences, University of Amsterdam, Science Park 904, 1098 XH, Amsterdam, The Netherlands.

Abstract

The tripodal, tetradentate tris(1-(diphenylphosphanyl)-3-methyl-1H-indol-2-yl)phosphane PP₃ -ligand 1 stabilizes Ru in the Ru^II , Ru^I , and Ru⁰ oxidation states. The octahedral [(PP₃ )Ru^II (Cl)₂ ] (2), distorted trigonal bipyramidal [(PP₃ )Ru^I (Cl)] (3), and trigonal bipyramidal [(PP₃ )Ru⁰ (N₂ )] (4) complexes were isolated and characterized by single-crystal X-ray diffraction, NMR, EPR, IR, and ESI-MS. Both open-shell metalloradical Ru^I complex 3 and the closed-shell Ru⁰ complex 4 undergo facile (net) abstraction of a Cl atom from dichloromethane, resulting in formation of the corresponding Ru^II and Ru^I complexes 2 and 3, respectively.

Keywords: chloride atom abstraction; dinitrogen complexes; metalloradicals; ruthenium; tripodal ligands.