The synthesis of a series of stable 8-alkoxyheptafulvene-Fe(CO)3 complexes V, VI and VIII from the appropriate acycloheptatriene-Fe(CO)3 complexes is described. Tetracyanoethylene cycloadds to complexes V and VIII in a 8 + 2 manner, giving X and XI respectively. Oxidation of X with cerium(IV) gives the tetrahydroazulene complex XIV. Similarly, N-phenyltriazolinedione reacts with V affording the imidoacetal adduct XII, which is readily hydrolyzed to form the water soluble imidoaldehyde complex XIII. 13C NMR studies indicate that the exocyclic double bond has no significant polar character.