title: Metal-Metal Interactions in Heterobimetallic Complexes with Dinucleating Redox-Active Ligands.
abstract: The tuning of metal-metal interactions in multinuclear assemblies is a challenge. Selective P coordination of a redox-active PNO ligand to Au(I) followed by homoleptic metalation of the NO pocket with Ni(II) affords a unique trinuclear Au-Ni-Au complex. This species features two antiferromagnetically coupled ligand-centered radicals and a double intramolecular d(8)-d(10) interaction, as supported by spectroscopic, single-crystal X-ray diffraction, and computational data. A corresponding cationic dinuclear Au-Ni analogue with a stronger d(8)-d(10) interaction is also reported. Although both heterobimetallic structures display rich electrochemistry, only the trinuclear Au-Ni-Au complex facilitates electrocatalytic C-X bond activation of alkyl halides in its doubly reduced state. Hence, the presence of a redox-active ligand framework, an available coordination site at gold, and the nature of the nickel-gold interaction appear to be essential for this reactivity.
authors.affiliation: van 't Hoff Institute for Molecular Sciences, University of Amsterdam, Science Park 904, 1098 XH, Amsterdam, The Netherlands.
authors.forename: Daniël L J
authors.initials: DL
authors.lastname: Broere
authors.affiliation: van 't Hoff Institute for Molecular Sciences, University of Amsterdam, Science Park 904, 1098 XH, Amsterdam, The Netherlands.
authors.forename: Dieuwertje K
authors.initials: DK
authors.lastname: Modder
authors.affiliation: van 't Hoff Institute for Molecular Sciences, University of Amsterdam, Science Park 904, 1098 XH, Amsterdam, The Netherlands.
authors.forename: Eva
authors.initials: E
authors.lastname: Blokker
authors.affiliation: Department of Chemistry, John Hopkins University, 3400 N, Charles St., Baltimore, MD, 21218, USA.
authors.forename: Maxime A
authors.initials: MA
authors.lastname: Siegler
authors.affiliation: van 't Hoff Institute for Molecular Sciences, University of Amsterdam, Science Park 904, 1098 XH, Amsterdam, The Netherlands. j.i.vandervlugt@uva.nl.
authors.forename: Jarl Ivar
authors.initials: JI
authors.lastname: van der Vlugt
keywords: gold; heterobimetallic complexes; metal-metal interactions; nickel; redox-active ligand