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Issue 23, 2014
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Heterobimetallic catechol-phosphine complexes with palladium and a group-13 element: structural flexibility and dynamics

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Abstract

Group-13 metal acetylacetonates [M(acac)3] (M = Al, Ga, In) or Al(OiPr)3 react with a complex [Pd(catphosH)2] that may act as chelating ligand towards a second metal, or with a mixture of catechol phosphine (catphosH2) and [PdCl2(cod)], to give heterometallic complexes featuring either dinuclear M(catphos)2Pd or trinuclear M{(catphos)2Pd}2 motifs. Characterisation of the products by crystallographic and solution NMR studies gives insight into the structural diversity and flexibility of the coordination environments of the group-13 elements and their impact on the stability of the multinuclear complexes. The results indicate that gallium and indium are the most suitable elements for the stabilisation of di- and trinuclear assemblies, respectively. Dynamic NMR spectroscopy allowed to follow the dynamic averaging of the coordination environments of the four distinguishable catechol phosphines in the indium complex [M{(catphos)2Pd}2]H. The results revealed that the isomerisation follows a complicated pathway involving several distinguishable proton transfer steps, and allowed to propose a mechanistic explanation for the observed isomerisation.

Graphical abstract: Heterobimetallic catechol-phosphine complexes with palladium and a group-13 element: structural flexibility and dynamics

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Publication details

The article was received on 15 Mar 2014, accepted on 30 Apr 2014 and first published on 30 Apr 2014


Article type: Paper
DOI: 10.1039/C4DT00785A
Citation: Dalton Trans., 2014,43, 8911-8920
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    Heterobimetallic catechol-phosphine complexes with palladium and a group-13 element: structural flexibility and dynamics

    G. Bauer, M. Nieger and D. Gudat, Dalton Trans., 2014, 43, 8911
    DOI: 10.1039/C4DT00785A

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