Ruthenium(II) complexes of a tripodal phosphite ligand: Synthesis, characterization, and applications in catalytic dehydrogenation

[Display omitted] •The coordination chemistry of a multidentate phosphite toward Ru(II) is studied.•The partial isomeric resolution using refluxing solvent is presented.•The structural elucidation of two isomers has been achieved.•The maximum denticity of the studied phosphite is observed for the fi...

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Veröffentlicht in:Inorganica Chimica Acta 2024-12, Vol.573, p.122314, Article 122314
Hauptverfasser: Rodríguez-Lugo, Rafael E., Chacón-Terán, Miguel A., Wolf, Robert, Landaeta, Vanessa R.
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Sprache:eng
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Zusammenfassung:[Display omitted] •The coordination chemistry of a multidentate phosphite toward Ru(II) is studied.•The partial isomeric resolution using refluxing solvent is presented.•The structural elucidation of two isomers has been achieved.•The maximum denticity of the studied phosphite is observed for the first time.•Additive-free dehydrogenation of formic acid or a secondary silane is investigated. The scaffold tris(8-quinolinyl)phosphite, (P(Oquin)3), can bind to metal centers as a bi- or a tridentate tripodal ligand, depending on the synthetic conditions and characteristics of the metal atom. Here the study of the coordinating properties of such chelate was extended to the synthesis and characterization of well-defined Ru(II)-halide complexes. The compound [κ3(N,P,N){P(Oquin)3}RuCl2(PPh3)] was obtained by simple ligand exchange on the precursor [(PPh3)3RuCl2]. Two isomers were observed by means of 31P{1H} NMR spectroscopy, and were partially separated by recrystallization in refluxing solvents, thus allowing their structure elucidation. X-ray diffraction analysis revealed that the two crystalline isomers have the formula [κ3(N,P,N){P(Oquin)3}RuCl2(PPh3)] with the phosphite ligand coordinated to the Ru(II) center either in a meridional or in a facial disposition. The mixture [κ3(N,P,N){P(Oquin)3}RuCl2(PPh3)] undergoes phosphine dissociation at temperatures over 100 °C, leading to the formation of [κ4(P,N3){P(Oquin)3}RuCl2]. This compound displays a tetradentate P(Oquin)3 chelate and is a suitable catalyst for the dehydrogenation of formic acid and the dehydrocoupling of methylphenylsilane.
ISSN:0020-1693
DOI:10.1016/j.ica.2024.122314