The indenyl iron compound (η5-C9H7)Fe(η5-C5H5) (1) was found to react with benzyne, generated from o-trimethylsilylphenyl triflate by fluoride-induced 1, 2-elimination, to afford the Diels-Alder adduct 1,2-(1,4-dihydro-naphthalen-1,4-diyl)ferrocene (2). When the bis-(indenyl) iron complexes (η5-R-C9H6)2Fe [R=H(3); 2-Me(6); 1-SiMe3(9)] reacted with benzyne, the bisadducts [R=H(5); 2-Me(8); 1-SiMe3(11)] were obtained along with the corresponding monoadducts [R=H(4); 2-Me(7); 1-SiMe3(10)]. The reaction of teramethyl-dislyene-bridged bis(indenyl) iron (Me2SiSiMe2)(η5-C9H6)2Fe(12) with benzyne gave only the monoadduct (13). Complex 2 was also tested for ring-opening metathesis polymerization (ROMP) in the presence of Grubbs' catalyst [(PCy3)2RuCl2=CHPh] but was found to be inactive under normal conditions. The molecular structures of 2, 5, 8, and 13 have been determinde by X-ray diffraction.