Photolysis of a hexane solution containing ironpentacarbonyl, 1-ferrocenyl-4-phenyl-1,3-butadiyne at low temperature yields six new products: [Fe(CO) 2 {η 2 :η 2 -PhCCCC(Fc)C(CCPh)C(Fc)Fe(CO) 3 }-μ-CO] (1), [Fe 2 (CO) 6 {μ-η 1 :η 1 :η 2 :η 2 -PhCCCC(Fc)–C(O)–C(Fc)CCCPh}] (2), [Fe 2 (CO) 6 {μ-η 1 :η 1 :η 2 :η 2 -FcCC(CC Ph)–C(O)–C(Fc)CCCPh}] (3), [Fe 2 (CO) 6 {μ-η 1 :η 1 :η 2 :η 2 -FcCCCC(Fc)–C(O)–C(Fc)CCCPh}] (4), [Fe(CO) 3 {μ-η 2 : η 2 -[FcCC(CCPh)C(CCPh)C(Fc)}CO] (5) and [Fe(CO) 3 {μ-η 2 : η 2 -[FcCC(CCPh)C(CCPh)C(Fc)}CO] (6) formed by coupling of acetylenic moieties with CO insertion on metal carbonyl support. In presence of CO, formation of another new product 2,5-bis(ferrocenyl)-3,6-bis(tetracarbonylphenylmaleoyliron)quinone (7) was observed which on further reaction with ferrocenylacetyene gave the quinone, 2,5-bis(ferrocenyl)-3,6-bis(ethynylphenyl)quinone (8). Structures of 1–5 and 8 were established crystallographically.