The complexes [(η 5 -C 5 H 5 )Fe(CO) 2 (SC≡CR)] (R= t Bu, SiMe 3 ) have been obtained by reaction of [(η 5 -C 5 H 5 )Fe(CO) 2 I] and the corresponding LiSC≡CR. These are the first examples of mononuclear iron compounds containing alkynethiolate ligands. The crystal structure of [(η 5 -C 5 H 5 )Fe(CO) 2 (SC≡CSiMe 3 )] has been determined by X-ray diffraction. The role of [(η 5 -C 5 H 5 )Fe(CO) 2 (SC≡CSiMe 3 )] as a metalloligand in its reactions with metal carbonyls has been explored.