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Known to be a facile irontncarbonyl transfer reagent, (11 2-cis-C sHI4hFe(CO)3 1 transfers its Fe(CO)3 unit to a variety of ligands at low temperature. Stirring a THF mixture of 1 and PhC=CPh under Nz(g) at -60 'C for 1 h then at room temperature overnight provides mainly a flyover-bridge product [-CPh=CPhC(O)-CPh=CPh-]FeiCO)6 2 with the organic bridge on diiron core in a complicated J.l-(1,2,5-11 3 : 1.4,5-11 l) fashion. The keto fragment in 2 comes presumably from the decomposition of 1 that liberates CO. However, stirring a THF mixture of 1 and PhC=CPh under CO (g) at -60· C for 3 h then at room temperature overnight results in [-C(O)CPh~CPhC(O)-]Fe(CO)4 3, a compound not isolated in theearlier thermal or photochemical reactions of PhC=CPh with ironcarbonyl. The X-ray structure determinations for both 2 and 3 have been performed.