Mechanistic Investigation of Cycloreversion/Cycloaddition Reactions between Zirconocene Metallacycle Complexes and Unsaturated Organic Substrates.

Treatment of the diazametallacycle Cp(2)Zr(N(t-Bu)C=N(SiMe(3))N(SiMe(3))) (4a) with diphenylacetylene resulted in the formation of the azametallacyclobutene Cp(2)Zr(N(t-Bu)C(Ph)=C(Ph)) (6a) and Me(3)SiN=C=NSiMe(3) in high yield. A kinetic study using UV-vis spectroscopy was carried out on the transformation. Saturation kinetic behavior was observed for the system, which is supportive of a mechanism that involves a reversible formal [2 + 2] retrocycloaddition of 4a to generate the transient imido species Cp(2)Zr=N-t-Bu (7a) and Me(3)-SiN=C=NSiMe(3). Trapping 7a with diphenylacetylene in an overall [2 + 2] cycloaddition reaction affords zirconacycle 6a. The study of cycloreversion/cycloaddition reactions between diazametallacycle complexes and diphenylacetylene was extended to other zirconocene systems. Detailed kinetic studies were performed for the exchange reactions between the diazametallacycle complexes Cp(2)Zr(N(2,6-Me(2)Ph)C=N(SiMe(3))N(SiMe(3))) (8a) and Cp(2)Zr-(N(2,6-Me(2)Ph)C=N(t-Bu)N(t-Bu)) (8b) with diphenylacetylene (5a) to give the corresponding azametallacyclobutene complex Cp(2)Zr(N(2,6-Me(2)Ph)C(Ph)=C(Ph)) (6c) and extruded carbodiimides (Me(3)SiN=C=NSiMe(3) for 8a and (t-Bu)N=C=N(t-Bu) for 8b). For both systems, the reactions were found to be first order in metallacycle and zero order in alkyne. Treatment of the diazametallacycle complexes Cp(2)Zr(N(2,6-i-Pr(2)Ph)C=N(Cyc)N(Cyc)) (9a) and Cp(2)Zr-(N(2,6-i-Pr(2)Ph)C=N(i-Pr(2))N(i-Pr(2))) (9b) with alkyne 5a resulted in the formation of the six-membered zirconacycles 10a,b, respectively, upon heating at 75 degrees C. The products 10a,b are generated from the overall insertion of alkyne 5a into the nitrogen-carbon bond of the zirconium-containing diazacyclobutane. Complex 10a has been characterized by an X-ray crystallographic study. When the azacyclobutene Cp(2)Zr(N(2,6-i-Pr(2)Ph)C(Ph)=C(Ph)) (6e) was treated with CycN=C=NCyc or (i-Pr)N=C=N(i-Pr), the same six-membered zirconacycle complexes 10a,b were obtained. Kinetic analysis of the reaction of 6e and (i-Pr)N=C=N(i-Pr) to yield 10b supports an associative process wherein alkyne 5a directly inserts into the zirconium-carbon bond of 6e. The diazametallacycle complex 4a underwent a stoichiometric metathetical exchange with symmetrical carbodiimides RN=C=NR (R = p-Tol, m-Tol, i-Pr, Cyc) to generate new cyclic zirconocene complexes and Me(3)SiN=C=NSiMe(3). Kinetic studies were carried out on the exchange reaction between 4a and (m-Tol)N=C=N(m-Tol) to form 4e and Me(3)SiN=C=NSiMe(3). The experimental rate data obtained are consistent with a dissociative mechanism. Additionally, the saturation rate constant derived for this system from the data is the same (within experimental error) as the saturation rate constant obtained from the kinetic study of 4a and diphenylacetylene to form 6a and Me(3)SiN=C=NSiMe(3). These findings provide additional support for a dissociative mechanistic pathway in the exchange reactions, since the rate constant in the formal [2 + 2] retrocycloaddition reaction to generate imidozirconocene species Cp(2)Zr=N-t-Bu (7a) and Me(3)SiN=C=NSiMe(3) should be the same for both reactions.