Synthesis and characterisation of N-coordinated pentafluorophenyl gold(I) thiazole-derived complexes and an unusual self-assembly to form a tetrameric gold(I) complex

Cronje S. ; Raubenheimer H.G. ; Spies H.S.C. ; Esterhuysen C. ; Schmidbaur H. ; Schier A. ; Kruger G.J. (2003)


Treatment of [Au(C6F5)(SC4H8)] (1) (SC4H8 = tetrahydrothiophene or tht) with HC=NC(CH3)=C(H)S, CH3SC=NC(CH3)=C(H)S, (I) or piperidine yields the neutral mononuclear imine complexes [Au(C6F5)-{N=C(H)SC(H)=CCH3}] (2) and [Au(C6F5){N=C(SCH3)SC(H)=CCH3}] (3), or the amine complex [Au(C6F5){N(H)CH2(CH2)3CH 2}] (4). The reaction of 1 with S=CN(H)C(CH3)=C(H)S, (II) affords the thione complex [Au(C6F5){S=CN(H)C(CH3)=C(H)S}] (5), which, in CH2Cl2 via spontaneous intermolecular deprotonation of the thione ligand, self-assembles to an unique tetramer of Au(I), [Au{S=CNC(CH3)=C(H)S}]4 (6) containing a folded rectangle of Au-atoms with aurophlilic interactions [av. Au ⋯ Au distance, 3.02(4) Å and av. Au-Au-Au angle, 87(2)°]. N-coordination of the imine complexes has been confirmed by 15N NMR and the crystal structure determination of 2 which exhibits the expected linear N-coordination and intermolecular Au ⋯ Au [3.345(1) Å] contacts. The crystal structure of 5 shows thione S-coordination of II to the central Au atom.

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