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


A series of alkynyl gold(I) tri and tetratopic metallaligands of the type [Au3(C≡C-R)3(μ3-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≡C-R)4(μ4-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 reaction between the alkynyl gold(I) polymeric species [Au(C≡C-R)]n and the adequate polyphosphane. An alternative strategy that required the previous synthesis of the appropriate acetylacetonate precursors [Aun(acac)n(μn-polyphosphane)] (“acac method”) was assayed, nevertheless only the polyacac derivatives [Au3(acac)3(μ3-triphosphane)] (triphosphane = triphos, triphosph) and [Au4(acac)4(μ4-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≡C-C10H7N2)4(μ4-tetraphos)] and [Au4(C≡C-C10H7N2)4(μ4-tpbz)] showed the involvement of all the gold atoms in close intramolecular Au···Au contacts 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 of cases the dangling units of the ligand have found to behave in a fairy independent way. While in the case of Cu(I) multiple equilibria exist in solution a single complex is detected for Zn(II) under the conditions studied.

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Publication details

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

    M. Ferrer, L. Giménez, A. Gutiérrez, J. C. C. Lima, L. Rodriguez, M. Martinez, A. Martín, R. Puttreddy and K. Rissanen, Dalton Trans., 2017, Accepted Manuscript , DOI: 10.1039/C7DT02732J

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