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有机化学
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有机化学 ›› 1986, Vol. 6 ›› Issue (6): 469-472. 上一篇    

研究论文

过渡金属氢化物和聚集双键化合物反应的研究IV.Cp~2Zr(H)Cl,(CP~2ZrH~2)~x与RNCO(R=C~H~5,α-C~10H~7)的反应

王梅;贝浼智;郭和夫   

  1. 中国科学院大连化学物理研究所
  • 发布日期:1986-12-25

Study on reaction of transition-metal hydrides with heterocumulenes IV. reaction of Cp2Zr(H)Cl, (Cp2ZrH2)x with rnco (R=C6H5, \a\-C10H7

WANG MEI;BEI MEIZHI;GUO HEFU   

  • Published:1986-12-25

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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,αC~10H~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~10H~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)~x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~10H~7)和化合物(CP~2ZrO)~3(6),RNH(CH~3)(7:R=C~6H~5;8:R=α-C~10H~7)及少量未知化合物.产物经元素分析,IR,^1H及^1^3C NMR和GC-MS谱分析鉴定.

关键词: 羧酸酯, 氢化物, 过渡金属化合物, 金属茂络合物, 加成反应, 脱氧, 异氰酸盐

Oxygen-bridging zirconocene complex (Cp2ZrCl)2O and Schiff base products RN=CH2 (R = Ph, a-naphthyl) were formed by reactions of Cp2Zr(H)Cl with phenyl- and a-naphthylisocyanate in C6H6 at 5~10? At 25~30? amines RNHMe, and a very small amount of RNHCONHR were also formed. However, when (Cp2ZrH2)x reacted with phenyl- and a-naphthylisocyanate both addition and deoxygenation reactions took place and yielded bidentate complexes I. These products were identified by elemental anal., IR, 1H & 13C NMR and GC-MS spectra, the differences between these two reactions and the reaction mechanisms were studied.

Key words: CARBOXYLIC ACID ESTER, HYDRIDES, TRANSITION METAL COMPOUND, METALLOCENES, ADDITION REACTION, DEOXIDIZATION, ISOCYANATE

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