Reaction of phenyl magnesium bromide with the α,β-unsaturated ketone 3-methyl-2,3,4,5,6,7-hexahydroind-8(9)-en-1-one, followed by an aqueous work-up, generates the pro-chiral tetra-substituted cyclopentadiene, 1-phenyl-3-methyl-4,5,6,7-tetrahydroindene, Cp ‡ H, a precursor to the η 5 -cyclopentadienyl ligand in (Cp ‡ ) 2 Fe and [(Cp ‡ )Fe(CO)] 2 (μ-CO) 2 . Both complexes were generated as mixtures of rac -( RR and SS )- and meso -( RS )-isomers, and in either case pure meso -isomer was isolated by crystallisation and characterised by single crystal X-ray structure, both molecules having crystallographic C i symmetry. Reduction with Na/Hg cleaves meso -( RS )-[(Cp ‡ )Fe(CO)] 2 (μ-CO) 2 and the resulting mixture of ( R )- and ( S )-[(Cp ‡ )Fe(CO) 2 ] − anions reacts with MeI to give racemic (Cp ‡ )Fe(CO) 2 Me, which was characterised by the X-ray crystal structure. The Cp ‡ ligand is more electron donating than (η-C 5 H 5 ) as revealed by the reduction potential of the (Cp ‡ ) 2 Fe + /(Cp ‡ ) 2 Fe couple, E °=−0.127 V (vs. Ag ∣ AgCl). Reaction of LiCp ‡ with ZrCl 4 yields the zirconocene dichloride [Zr(Cp ‡ ) 2 Cl 2 ] as mixture of rac - and meso -isomers, from which pure rac -isomer is obtained as a mixture of RR and SS crystals by recrystallisation. The reaction of rac -[Zr(Cp ‡ ) 2 Cl 2 ] with LiMe gives rac -[Zr(Cp ‡ ) 2 Me 2 ]. The structures of RR -[Zr(Cp ‡ ) 2 Cl 2 ] and rac -[Zr(Cp ‡ ) 2 Me 2 ] have been determined by X-ray diffraction. The structural studies reveal the influence of the bulky substituted cyclopentadienyl ligand on the metalCp ‡ distances and other metric parameters.