Abstract
The ability of 3‐(diphenylphosphinomethyl)‐benzene‐1,2‐dithiol (pbdtH2) to act as ditopic ligand was probed in reactions with selected group‐10‐metal complexes. Reactions with [(cod)PdCl2] afforded a mixture of products identified as [Pd(pbdtH)2], [Pd2(μ2‐pbdt)2] and [Pd3(μ2‐pbdt)2Cl2]. The polynuclear complexes could be isolated after suitably adjusting the reaction conditions, and heating of a mixture in a microwave reactor effected partial conversion into a further complex [Pd3(μ2‐pbdt)3]. Reaction of pbdtH2 with [Ni(H2O)6Cl2] gave rise to a complex [Ni2(μ2‐pbdt)2], which was shown to undergo two reversible 1e–‐reduction steps. Reaction of [Pd(pbdtH)2] with [Au(PPh3)Cl] afforded heterotrinuclear [PdAu2(μ2‐pbdt)2(PPh3)]. All complexes were characterized by analytical, spectroscopic and single‐crystal X‐ray diffraction studies. Their molecular structures confirm the ability of the pbdt2– unit to support simultaneous P,S‐ and S,S‐chelating coordination to two metal centers.
Highlights
Ditopic ligands possess multiple donor functions that are arranged to provide separate binding domains for two metal centers and enable the assembly of elaborate architectures from di- and multinuclear complexes with specific molecular geometries[1] to coordination polymers and more-dimensional framework structures.[2]
We report on an extended study of the complexation behavior of 2, which reveals that the free ligand and its palladium complex 3 can be used as scaffolds for the assembly of homo- or heterometallic complexes with two or three metal centers
Of a tailored precursor with a predisposition to react under successive displacement of the acac– units by new mono-anionic chelate ligands, and the maintenance of a metal-to-ligand ratio of 1:2 needed for exhaustive ligand exchange.[4]
Summary
Ditopic ligands possess multiple donor functions that are arranged to provide separate binding domains for two metal centers and enable the assembly of elaborate architectures from di- and multinuclear complexes with specific molecular geometries[1] to coordination polymers and more-dimensional framework structures.[2]. The corresponding reaction of 2 with [Ni(acac)2] was less selective and afforded, according to a 31P NMR spectroscopic assay, a mixture of several newly formed species, one of which was later on identified as a 2:2 complex composed of two metal cations and two dianionic pdbt2– ligands (see below).
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