1, 1′-Diisocyanoferrocene (1) reacts coordinatively with [Au (C Cp-C6H4R)] n (2a R= CF3, 2b R= H, 2c R= OMe, 2d R= NMe2) to afford the gold complexes [{Au (C Cp-C6H4R)} 2 (μ-1)](3), whose aurophilic aggregation in the crystal depends on the nature of R. The two chemically equivalent functional groups of 1 each undergo a different specific reaction with [Au (C C-Fc)] n (2e, Fc= ferrocenyl), viz., orthodox coordination and unorthodox 1, 1- ...