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Updated: Sep 2, 2025

The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes
Published on: April 10, 2015
Heterobimetallic Gold/Ruthenium Complexes Synthesized via Post-functionalization and Applied in Dual Photoredox Gold
Lea Bayer1, Bernhard S Birenheide1, Felix Krämer1
1Karlsruhe Institute of Technology (KIT), Institute of Inorganic Chemistry, Division Molecular Chemistry, Engesserstraße 15, 76131, Karlsruhe, Germany.
Abstract:
The synthesis of heterobimetallic AuI /RuII complexes of the general formula syn- and anti-[{AuCl}(L1∩L2){Ru(bpy)2 }][PF6 ]2 is reported. The ditopic bridging ligand L1∩L2 refers to a P,N hybrid ligand composed of phosphine and bipyridine substructures, which was obtained via a post-functionalization strategy based on Diels-Alder reaction between a phosphole and a maleimide moiety. It was found that the stereochemistry at the phosphorus atom of the resulting 7-phosphanorbornene backbone can be controlled by executing the metal coordination and the cycloaddition reaction in a different order. All precursors, as well as the mono- and multimetallic complexes, were isolated and fully characterized by various spectroscopic methods such as NMR, IR, and UV-vis spectroscopy as well as cyclic voltammetry. Photophysical measurements show efficient phosphorescence for the investigated monometallic complex anti-[(L1∩L2){Ru(bpy)2 }][PF6 ]2 and the bimetallic analogue syn-[{AuCl}(L1∩L2){Ru(bpy)2 }][PF6 ]2 , thus indicating a small influence of the {AuCl} fragment on the photoluminescence properties. The heterobimetallic AuI /RuII complexes syn- and anti-[{AuCl}(L1∩L2){Ru(bpy)2 }][PF6 ]2 are both active catalysts in the P-arylation of aryldiazonium salts promoted by visible light with H-phosphonate affording arylphosphonates in yields of up to 91 %. Both dinuclear complexes outperform their monometallic counterparts.
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