Synthesis, Characterization And Reactions Of Aluminacyclobutene

Reaction of (LAl[η²-(CPh)₂] (L = HC[(CMe)(NAr)]₂, Ar = 2, 6-'Pr₂C₆H₃) , 4) with carbon monoxide at room temperature afforded aluminacyclobutene (LAl[C(O)C₂Ph₂] L = HC[(CMe)(NAr)]₂, Ar = 2, 6-'Pr₂C₆H₃, 5) . We testified the carbonyl of compound 5 is a terminal "acyl anion" by reaction of 5 with diphenylketone in toluene at room temperature afforded compound ((LAl[OC(Ph)₂C(O)C₂Ph₂] L = HC[(CMe)(NAr)]₂, Ar = 2, 6-'Pr₂C₆H₃) , 6) . Reaction of 5 with phenyl cyanide in toluene at room temperature formed compound 8 (LAl[N=CPhC(O)C₂Ph₂] , L HC(CMeNAr), Ar = 2, 6-'Pr₂C₆H₃) . Reaction of5 with MeSiCN at-78℃afforded compound 7 which containing a "cycloprotene" structure. Compound 5 reacted with dioxygen, sulfur respectively obtained LAl[OC(O)CPh], (L = HC[(CMe)(NAr)]₂, Ar = 2, 6-'Pr₂C₆H₃, 9) and LAl[SC(O)C₂Ph₂] , (L = HC[(CMe)(NAr)]₂, Ar = 2, 6-'Pr₂C₆H₃,10) . IR, Element Analysis, ¹H and ¹³ C NMR and EI-MS were employed to characterize these complexes. The molecular structures of 5, 6 and 7 were detected by X-ray single crystal diffraction analysis.Alkylaluminum Complexes 11 and 12 with (2-dimethylamino -5-methylphenyl) diphenylcarbinol were prepared under a purified nitrogen atmosphere and characterized by IR, ¹H NMR and ¹³ C NMR.