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Updated: Aug 2, 2025
The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes
Published on: April 10, 2015
Hydroxypyridine/Pyridone Interconversions within Ruthenium Complexes and Their Application in the Catalytic
Ramaraj Ayyappan1, Uttam Kumar Das1, Issam Abdalghani1
1School of Applied Sciences, University of South Wales, Pontypridd CF37 4AT, U.K.
Abstract:
Reaction of a new ligand 6-DPPon (6-diisopropylphosphino-2-pyridone) with 0.5 equiv of [RuCl2(p-cymene)]2 resulted in the formation of a mixture of [RuCl2(p-cymene)(κ1-P-6-DPPon)]2 (1) and [RuCl(p-cymene)(κ2-P,N-6-DPPin)]Cl ([2]Cl) (where 6-DPPin = 6-diisopropylphosphino-2-hydroxypyridine). The ratio between the two products can be controlled by the nature of the solvent. The similar reaction between 6-DPPon and [RuCl2(p-cymene)]2 in the presence of AgOTf and Na[BArF24] (where BArF24 = [{3,5-(CF3)2C6H3}4B]-) resulted in the formation of the complexes [RuCl(p-cymene)(κ2-P,N-6-DPPin)]OTf, ([2]OTf) and [RuCl(p-cymene)(κ2-P,N-6-DPPin)]BArF24 ([2]BArF), respectively. Reactions between complex [2]Cl, [2]OTf, or [2]BArF and a base (either DBU or NaOMe) resulted in the deprotonation of the hydroxyl functional group to form a novel neutral orange-colored dearomatized complex, 3. The identity of complex 3 was confirmed as [RuCl(p-cymene)(κ2-P,N-6-DPPon*)], where 6-DPPon* is the anionic species (6-diisopropylphosphino-2-oxo-pyridinide), which contains the deprotonated moiety. The new 6-DPPon ligand and its corresponding air stable half-sandwich derivative ruthenium complexes 1, [2]OTf, [2]BArF, and 3 were all isolated in good yields and fully characterized by spectroscopic and analytical methods. The interconversions between the neutral and anionic forms of the ligands 6-DPPon, 6-DPPin, and 6-DPPon* offer the potential for novel secondary sphere interactions and proton shuttling reactivity. The consequences for this have been explored in the activation of H2 and the subsequent catalytic hydrogenations of CO2 into formate salts in the presence of a base.
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