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Metal–Metal Interactions in Heterobimetallic Complexes with Dinucleating Redox‐Active Ligands
Author(s) -
Broere Daniël L. J.,
Modder Dieuwertje K.,
Blokker Eva,
Siegler Maxime A.,
van der Vlugt Jarl Ivar
Publication year - 2016
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201509412
Subject(s) - chemistry , homoleptic , ligand (biochemistry) , metalation , intramolecular force , redox , reactivity (psychology) , metal , nickel , cationic polymerization , crystallography , oxidation state , crystal structure , stereochemistry , photochemistry , inorganic chemistry , polymer chemistry , organic chemistry , medicine , biochemistry , receptor , alternative medicine , pathology
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.