Reduction of Zr(η 5-C 5H 5)(η 5-1,3- t Bu 2C 5H 3)Cl 2 with 1.5 equiv of 10% sodium amalgam in toluene affords the zirconium(III) derivative [Zr(η 5-1,3- t Bu 2C 5H 3)(μ-Cl)] 2(μ-η 5-η 5-C 10H 8) ( 1) which reacts with chlorine or chlorinated solvents to give the zirconium(IV) compound [Zr(η 5-1,3- t Bu 2C 5H 3)Cl 2] 2(μ-η 5-η 5-C 10H 8) ( 2). When the tetrachloro fulvalene [ZrCp′Cl 2] 2(μ-η 5-η 5-C 10H 8) (Cp′=η 5-C 5H 5 (Herrmann et al., Angew. Chem. Int. Ed. Engl. 26 (1987) 697); η 5-1,3- t Bu 2C 5H 3 ( 2)) compounds were treated with four equivalents of LiR (R=Me, Ph) in toluene at −78 °C the tetraalkyl derivatives [ZrCp′R 2] 2(μ-η 5-η 5-C 10H 8) (Cp′=η 5-C 5H 5, R=Me, Ph ( 3); η 5-1,3- t Bu 2C 5H 3, R=Me ( 4)) were obtained. Compound 4 reacts with a stoichiometric amount of water with hydrolysis of the Zr–methyl bond to give the μ-oxo complex [Zr(η 5-1,3- t Bu 2C 5H 3)(CH 3)] 2(μ-O)(μ-η 5-η 5-C 10H 8) ( 8). The zirconium alkoxide [Zr(η 5-C 5H 5)(η 2-O 2SiPh 2)] 2(μ-η 5-η 5-C 10H 8) ( 5) and the iminoacyl complexes [Zr(η 5-C 5H 5){η 2-CRN(2,6-Me 2C 6H 3)}R] 2(μ-η 5-η 5-C 10H 8) (R=Me ( 6), Ph ( 7)) were prepared by reaction of the tetraalkyl complexes with either the alcohol Ph 2Si(OH) 2 or isocyanide CN(2,6-Me 2C 6H 3), respectively. Two diastereoisomers of compounds 6 and 7 were obtained.