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Updated: Jun 9, 2025

The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes
Published on: April 10, 2015
Ruthenium, copper and ruthenium-copper complexes of an unsymmetrical phosphino pyridyl 1,8-naphthyridine PNNN ligand
Jingyun Wu1, Michael A Stevens1, Michael G Gardiner1
1Research School of Chemistry, Australian National University, Canberra, ACT, 2601, Australia. annie.colebatch@anu.edu.au.
Abstract:
A new unsymmetrical dinucleating phosphino pyridyl 1,8-naphthyridine ligand PNNN is reported. Reaction with CuCl gave the dicopper complex [Cu2(μ-Cl)2(PNNN)] (1). In contrast, complexation of [RuCl2(cymene)]2 yielded a monometallic species [RuCl(cymene)(PNNN)]Cl ([2]Cl) in which the Ru is bound to the κ2-N,N, rather than κ2-P,N, binding pocket. The selective formation of the monoruthenium complex [2]Cl enabled synthesis of heterobimetallic complexes [RuCuCl3(cymene)(PNNN)] (3) and [RuCuCl2(cymene)(PNNN)]2[PF6]2 ([4]2[PF6]2), which both exhibit κ1-P coordination of Cu. Complexes 1 and [4]2[PF6]2 exhibit reversible dearomatisation-aromatisation behaviour at the metal-ligand cooperative methylene site upon sequential treatment with base (KOBu) and acid (HCl). Notably, deprotonation of [4]2[PF6]2 induces a shift in the coordination mode of Cu to κ2-P,N.
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