The reactivity of Cp(2)CTHF)Zr-N-r-Bu (la) toward a series of organic and metal carbonyl complexes has been examined. The Zr=N linkage of la undergoes imido/oxo exchange reactions with the carbonyl compounds and generates three different types of oxozirconocene products : (Cp(2)Zr=O)(n) (3), (Cp(2)Zr)(2)(mu-O)(mu-N-t-Bu) (9), (a)nd (Cp(2)Zr)(2)O(3)CCPh(2) (12) were obtained from the reactions of 1a with RR’C=O (R = R’ = Me (2b); R = Ph, R’ = H (2c); R = i-Pr, R’ = H (2d)), CpCo(CO)2 (7), and Ph(2)C=C=O (10), respectively. The coproducts in these reactions were imines RR’C=N-t-Bu (4b-d), isonitrile complexes CpCo(CO)(CN-t-Bu) (8a), and ketenimines Ph(2)C=C=Nt-Bu (11a), respectively. With more highly hindered carbonyls containing a-hydrogen atoms, the reaction followed a different pathway leading to the formation of the enolate complexes Cp(2)Zr(NH-t-Bu)(OCR(3)CR(2)R(1)) (R(1) = H, R(2) and R(3) = (CH2)(3)CH(CCH3)(3) (5e); R(1) = R(2) = H, R(3) = C(CH3)(3) (5f); R(1) = R(2) = CH3, R(3) = CH(CH3)(2) (5g)). Possible mechanisms for these transformations, as well as the factors that might control the dependence of the fate of "Cp(2)Zr=O" on its method of generation, are discussed.