Reactivity of Zirconocene Azametallacyclobutenes: Insertion of Aldehydes, Carbon Monoxide, and Formation of alpha,beta-Unsaturated Imines. Formation and Trapping of [Cp(2)Zr=O] in a [4 + 2] Retrocycloaddition(1).

Azametallacyclobutene Cp(2)ZrN-t-BuCEt=CEt (1) underwent an insertion reaction with CO to form the acyl complex 2 (Cp(2)Zr(N-t-BuCEtCEtCO), 67% yield). The addition of acetone to azametallacyclobutene 3 (Cp(2)Zr(NArCMeCPh), Ar = 2,6-dimethylphenyl) yielded the N-bonded enamine and O-bonded enolate complex of zirconocene 4 (Cp(2)Zr(NArCMeCPhH)(OCMeCH(2)), 76% yield). The addition of aldehydes RCOH to metallacycle 3 resulted in the insertion of the aldehyde into the Zr-C bond to form complexes Cp(2)Zr(NArCMeCPhCRHO) (8a) and Cp(2)Zr(NArCMeCPhC(i-Pr)HO (9) in 85% (R = Ph) and 73% yields, respectively. Similarly, treatment of metallacycle 10 (Cp(2)Zr(NArCEtCEt)) with benzaldehyde yielded the insertion product 11 (Cp(2)Zr(NArCEtCEtCPhHO)) in 56% isolated yield. The structure of complex 11 was confirmed by an X-ray crystallographic study. Heating the insertion products 8a and 9 led to elimination of the alpha,beta-unsaturated imines 13 and 14a (ArN=CMeCPh=CRH) in 53% and 72% yields, respectively, and the formation of oxozirconocene oligomer (Cp(2)ZrO)(n)(). The oxozirconocene monomer was trapped by dimethylzirconocene, preventing the formation of oligomer and resulting in the isolation of product 15. A kinetic study of this retrocycloaddition produced the following activation parameters: DeltaH() = 26.5 kcal/mol, DeltaS() = 3.48 eu. A Hammett sigma/rho study showed that electron-donating groups alpha to the metallacycle oxygen accelerate the retrocycloaddition (rho = -0.8).