Fascinating chemistry of mutually compatible symmetrical/ asymmetrical and bulky heterocyclic β-diketones- modified zirconocene dichloride: DFT assisted optimized molecular structure of C33H32N2O4Zr containing two unequal Zr-Cp bonds

Abstract

Mutually compatible bulky heterocyclic β-diketones and symmetrical/ asymmetrical β-diketones- modified zirconocene dichloride products of the general formula [Cp₂ZrLL’] (where LH=  and L’H= R’COCH₂COR”, R= -CH₃ (L₍₁₎H), R=  -CH₂CH₃ (L₍₂₎H), R=  -C₆H₅ (L₍₃₎H), R= p-ClC₆H₄- (L₍₄₎H) and R’= R”= -CH₃ (L’₍₁₎H), R’= -CH₃, R”= -C₆H₅ (L’₍₂₎H), R’= R”= -C₆H₅ (L’₍₃₎H)) were generated by the reactions of zirconocene dichloride with mutually compatible bulky heterocyclic β-diketones and symmetrical/ asymmetrical β-diketones in the presence of triethylamine in 1:1:1:2 molar ratio in refluxing dry THF. On the basis of spectroscopic and mass studies, tentative structures of these complexes were suggested. Density functional theory (B3LYP) was employed to study the optimized molecular structure, optimized energy, stability, distortions of optimized geometry and energy gap of one representative zirconocene complex to corroborate the structures of these complexes.