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Issue 2, 2013
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Cis and trans-bis(tetrathiafulvalene-acetylide) platinum(II) complexes: syntheses, crystal structures, and influence of the ancillary ligands on their electronic properties

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Abstract

A series of four platinum(II) complexes bearing two tetrathiafulvalene acetylide ligands coordinated either cis or trans to the metal center are reported: cis-Pt(bipy)(C[triple bond, length as m-dash]CMe3TTF)2, cis-Pt(tBu2bipy)(C[triple bond, length as m-dash]CMe3TTF)2, cis-Pt(dppe)(C[triple bond, length as m-dash]CMe3TTF)2 and trans-Pt(PPh3)2(C[triple bond, length as m-dash]CMe3TTF)2. The X-ray diffraction studies of the four complexes are reported and discussed. The electrochemical investigations carried out by cyclic voltammetry (CV) and differential pulse voltammetry (DPV) evidenced different redox behavior as a function of the ancillary ligand. Only for the cis-Pt(dppe)(C[triple bond, length as m-dash]CMe3TTF)2 complex is the first oxidation wave resolved (ΔE = 70 mV) into two one-electron processes. Spectroelectrochemical investigations performed on the four complexes did not evidence any electronic interactions between the two organic electrophores. The splitting of the first oxidation wave observed in cis-Pt(dppe)(C[triple bond, length as m-dash]CMe3TTF)2 is mainly explained by the non-equivalence of the two TTF moieties induced by the geometrical constraint imposed by the ancillary dppe ligand as found by density functional theory calculations.

Graphical abstract: Cis and trans-bis(tetrathiafulvalene-acetylide) platinum(ii) complexes: syntheses, crystal structures, and influence of the ancillary ligands on their electronic properties

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Publication details

The article was received on 26 Jul 2012, accepted on 21 Sep 2012 and first published on 24 Sep 2012


Article type: Paper
DOI: 10.1039/C2DT31686B
Citation: Dalton Trans., 2013,42, 383-394
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    Cis and trans-bis(tetrathiafulvalene-acetylide) platinum(II) complexes: syntheses, crystal structures, and influence of the ancillary ligands on their electronic properties

    A. Vacher, F. Barrière, F. Camerel, J. Bergamini, T. Roisnel and D. Lorcy, Dalton Trans., 2013, 42, 383
    DOI: 10.1039/C2DT31686B

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