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Polypyridyl-functionalizated alkynyl gold(I) metallaligands supported by tri- and tetradentate phosphanes

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A series of alkynyl gold(I) tri and tetratopic metallaligands of the type [Au3(C[triple bond, length as m-dash]C–R)33-triphosphane)] (R = 2,2′-bipyridin-5-yl or C10H7N2, 2,2′:6′,2′′-terpyridin-4-yl or C15H10N3; triphosphane = 1,1,1-tris(diphenylphosphanyl)ethane or triphos, 1,3,5-tris(diphenylphosphanyl)benzene or triphosph) and [Au4(C[triple bond, length as m-dash]C–R)44-tetraphosphane)] (R = C10H7N2, C15H10N3; tetraphosphane = tetrakis(diphenylphosphanylmethyl)methane or tetraphos, 1,2,3,5-tetrakis(diphenylphosphanyl)benzene or tpbz, tetrakis(diphenylphosphaneylmethyl)-1,2-ethylenediamine or dppeda) were obtained in moderate to good yields. All complexes could be prepared by a reaction between the alkynyl gold(I) polymeric species [Au(C[triple bond, length as m-dash]C–R)]n and the appropriate polyphosphane. An alternative strategy that required the previous synthesis of the appropriate acetylacetonate precursors [Aun(acac)nn-polyphosphane)] (“acac method”) was assayed, nevertheless only the polyacac derivatives [Au3(acac)33-triphosphane)] (triphosphane = triphos and triphosph) and [Au4(acac)44-tetraphos)] could be isolated and characterized. All compounds were characterized by IR, multinuclear NMR spectroscopy and ESI(+) mass spectrometry. The X-ray crystal structure of complexes [Au4(C[triple bond, length as m-dash]C–C10H7N2)44-tetraphos)] and [Au4(C[triple bond, length as m-dash]C–C10H7N2)44-tpbz)] showed the involvement of all the gold atoms in close intramolecular Au⋯Au contact as well as intermolecular π stacking interactions between the aromatic rings of the polypyridyl ligands. The photophysical properties of the synthesized compounds were carefully studied and used as a probe of their possible use as multidentate ligands for Cu(I) and Zn(II). The UV-Vis speciation studies of the complexation reactions were conducted via metal titration and, in most cases the dangling units of the ligand were found to behave in a fairy independent manner. While in the case of Cu(I) multiple equilibria exist in solution a single complex is detected for Zn(II) under the conditions studied.

Graphical abstract: Polypyridyl-functionalizated alkynyl gold(i) metallaligands supported by tri- and tetradentate phosphanes

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The article was received on 26 Jul 2017, accepted on 12 Sep 2017 and first published on 14 Sep 2017

Article type: Paper
DOI: 10.1039/C7DT02732J
Citation: Dalton Trans., 2017, Advance Article
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    Polypyridyl-functionalizated alkynyl gold(I) metallaligands supported by tri- and tetradentate phosphanes

    M. Ferrer, L. Giménez, A. Gutiérrez, J. C. Lima, M. Martínez, L. Rodríguez, A. Martín, R. Puttreddy and K. Rissanen, Dalton Trans., 2017, Advance Article , DOI: 10.1039/C7DT02732J

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