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本文报道了二茂锆氢化物与异氰酸酯在不同条件下的反应。Cp_2Zr(H)Cl与RNCO(R=C_6H_5,α-C_(10)H_7)在苯中,5～10℃下反应,生成锆的氧桥络合物(Cp_2ZrCl)_2O(1)和Schiff碱型化合物RN=CH_2(2:R=C_6H_5;3:R=α-C_(10)H_7)。当反应在25～30℃下进行时,还有少量有机胺RNH(CH_3)及很少量的RNHCONHR生成。而(Cp_2ZrH_2)_(?)与RNCO反应时,同时发生加成和脱氧两种反应,生成双齿配位络合物Cp_2Zr(H)[RN=C(H)=O](4:R=C_6H_5;5:R=α-C_(10)H_7)和化合物(Cp_2ZrO)_3(6)、RNH.(CH_3)(7:R=C_6H_5;8:R=α-C_(10)H_7)及少量未知化合物。产物经元素分析、IR、~1H及~(13)C NMR和GC-Ms谱分析鉴定。
This paper reports the reaction of zirconocene hydrides with isocyanates under different conditions. The reaction of Cp_2Zr (H) Cl with RNCO (R = C_6H_5, α-C_ (10) H_7) in benzene at 5 ~ 10 ℃ yields the oxadiazole complex of zirconium (Cp_2ZrCl_2O_ (1) Compound RN = CH 2 (2: R = C_6H_5; 3: R = α-C_ (10) H_7). Small amounts of organic amine RNH (CH 3) and very small amounts of RNHCONHR are also formed when the reaction is carried out at 25-30 ° C. When (Cp_2ZrH_2) _ (?) Reacts with RNCO, two kinds of reactions of addition and deoxidation occur at the same time, and the bidentate complex Cp_2Zr (H) [RN = C (H) (CH_3) (7: R = C_6H_5; 8: R = α-C_ (10) H_7) and a small amount of compounds (C_6H_5; 5: R = α-C_10H_7) Unknown compound. The product was identified by elemental analysis, IR, ~ 1H and ~ (13) C NMR and GC-Ms spectral analyzes.