Photolysis of a hexane soln. contg. iron pentacarbonyl, 1-ferrocenyl-4-phenyl-1,3-butadiyne at low temp. yields six new products: [Fe(CO)2{η2:η2-PhC≡CCC(Fc)C(C≡CPh)C(Fc)Fe(CO)3}-μ-CO] (1), [Fe2(CO)6{μ-η1:η1:η2:η2-PhC≡CCC(Fc)-C(O)-C(Fc)CC≡CPh}] (2), [Fe2(CO)6{μ-η1:η1:η2:η2-FcCC(C≡C Ph)-C(O)-C(Fc)CC≡CPh}] (3), [Fe2(CO)6{μ-η1:η1:η2:η2-FcC≡CCC(Fc)-C(O)-C(Fc)CC≡CPh}] (4), [Fe(CO)3{μ-η2:η2-FcCC(C≡CPh)C(C≡CPh)C(Fc)}CO] (5) and [Fe(CO)3{μ-η2:η2-FcCC(C≡CPh)C(C≡CPh)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 obsd. 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 crystallog. [on SciFinder(R)]