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The reaction of N,N′-bis(trimethylsilyl)carbodiimide with equimolar quantities of tris[(triphenylphosphine)gold]oxonium tetrafluoroborate in dichloromethane at -40°C gives high yields of a trinuclear complex {[(Ph 3 P)Au] 2 NCN[Au(PPh 3 )]} +  BF 4  - (1). According to variable temperature NMR data the cation is fluxional in solution with a rapid site exchange of the [(Ph 3 P)Au] units, but has an unsymmetrical (N,N,N′) low temperature ground state configuration. A single crystal X-ray diffraction study has shown that in the crystal lattice these cations are associated further into cyclic, hexanuclear dimers through two short head-to-tail Au-Au contacts (auriophilicity). Treatment of complex 1 with one equivalent of [(Ph 3 P)Au] +  BF 4  -  in tetrahydrofuran affords a tetranuclear complex {[(Ph 3 P)Au] 2 NCN[Au(PPh 3 )] 2 } 2+  2BF 4  -  (2). The ambient temperature NMR spectra of 2 suggest a fluxional, pseudo-symmetrical structure, but at low temperature a set of three  31 P signals (1:2:3 intensity) indicates an aggregation into higher nuclearity species with non-equivalent [Au(PPh 3 )] units

Polynuclear Gold Complexes of the Carbodiimide Unit [N=C=N] 2-