Alcoholysis And Addition To Aldehyde(or Ketone) Carbonyls And Nitrile Of Hydrozincation Reagent [{HC(CMeNAr)₂}Zn(μ-H)]₂, As Well As Its Application In Ring-Opening Polyerization Of Lactide And ε-Carploctone

Reductive hydrozincation of acetone and benzaldehyde with hydrozincation reagent [{HC(CMeNAr)₂}Zn(μ-H)]₂ (Ar = 2,6-Me₂C₆H₃, 4), afforded compound [{HC(CMeNAr)₂}Zn(μ-OR)]₂ (R = ⁱPr, 5; R = Bn, 6). Compound 6 was also readily obtained by treating 4 with 2 equiv of benzyl alcohol. Alcoholysis of 4 with methanol and phenol resulted in [{HC(CMeNAr)₂}Zn(μ-OR)]₂ (R = Ph, 7; R = Me, 8) respectively. Hydrozincationof Benzonitrile by 4 led to a diimino-brdiged zinc complexes [{HC (CMeNAr)₂}Zn(μ-N=CHPh)]₂ (9) in high yield. Complexes 5-8 were characterized by FT-IR and ¹H NMR. The structures of 8 and 9 were determined by X-Ray single crystal analysis.Hydrozincation reagent 4 had been employed as an initiator for ring-open polymerization of lactide and e-caprolactone. It was showed that the optimized catalytsis condition for 4 was at 60℃in toluene, displaying a living ROP feature. Kinetic studies of 4 for ROP of e-caprolactone indicate that the polymerization is the first order. The diketiminatozinc alkoxides 5-8 were also tested to be active initiators for ROP of lactide andε-caprolactone. And Kinetic studies of 6 for ROP ofε-caprolactone indicate that the polymerization of also the first order.