Synthesis and characterisation of Pd(ii) and Au(i) complexes with mesoionic carbene ligands bearing phosphinoferrocene substituents and isomeric carbene moieites.

While numerous functional ligands combining phosphine and imidazole-2-ylidene (or imidazolin-2-ylidene) donor moieties have already been reported, the chemistry of the corresponding functional mesoionic carbenes (MIC) derived from 1,2,3-triazoles remains nearly untapped. This contribution describes the synthesis of two isomeric series of triazolium salts bearing 1'-(diphenylphosphino)ferrocenyl substituents by [3 + 2] cycloaddition of a P-protected phosphinoferrocene alkyne with azides, or alternatively of a P-protected phosphinoferrocene azide with terminal alkynes, and by subsequent methylation. These salts were used to synthesize structurally unique Pd(ii) complexes featuring a P,C-chelating triazolylidene carbene ligands and Au(i)-MIC complexes with free phosphine groups. The latter were further utilised to prepare Pd(ii)Au(i) heterometallic complexes containing bridging ferrocene phosphino-carbenes as structurally flexible, donor-unsymmetric metalloligands. In addition, the reactivity of the newly prepared, P-protected phosphinoferrocene alkyne Ph2PfcC[triple bond, length as m-dash]CH·BH3 (fc = ferrocene-1,1'-diyl) was investigated, and representatives from all reported compound classes were structurally characterised.