A systematic study into the Sonogashira cross-coupling of 1,1'-diiodoferrocene (fcI2) confirms that the Pd(0)-P((t)Bu)3 system provides a remarkable rate increase over Pd(0)-(PPh3)2. Attempts to couple 4-ethynylphenylthioacetate (2) with fcI2 instead produced a novel cyclic trimer of the former, from syn addition of S-Ac across C≡C.