The photolytic reaction of (Z)-1-ferrocenyltelluro-1-ferrocenyl-4-ferrocenyl-1-buten-3-yne with iron pentacarbonyl in hexane gives the tellurium coordinated carbonyl vinylallyl dinuclear iron complex 1, tellurium coordinated vinylallyl trinuclear iron complex 2, a lactone fused ferracyclopentadiene complex 3, and a butterfly complex 4. On reaction with PPh₃, 1 undergoes fragmentation to yield a cyclopentadienone (7) and the starting material (Z)-1-ferrocenyltelluro-1-ferrocenyl-4-ferrocenyl-1-buten-3-yne. In addition, reactions of the tellurium ene-yne ligand with [M(CO)₅(THF)] or [M(CO)₆] give the M(CO)₅ adducts 8–10. All compounds have been characterized by IR, ¹H NMR and ¹³C NMR spectroscopy and structures of 1–4 and 7 have been established by single crystal X-ray diffraction.