Synthesis and characterization of some zirconium and hafnium complexes with a phosphide-pendant cyclopentadienyl ligand
Synthesis and characterization of some zirconium and hafnium complexes with a phosphide-pendant cyclopentadienyl ligand
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DOI：
10.1021/om020916
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发表时间：
2003-01
期刊：
影响因子：
2.8
通讯作者：
T. Ishiyama;Tsutomu Mizuta;K. Miyoshi;H. Nakazawa
中科院分区：
文献类型：
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作者：
T. Ishiyama;Tsutomu Mizuta;K. Miyoshi;H. Nakazawa
通过烷基化（三苄基化、三烯丙基化或单三苯甲基化）二次膦侧基的配体[{η5-C5 H4（CH 2）2 P（H）Mes-κP} MCl 3（tht）]（Zr-1，Hf-1; Mes = 2，4，6-三甲基苯基; tht =四氢噻吩），尝试合成一些具有膦侧基的配体的Zr和Hf配合物。分别以Zr-1和Hf-1为原料，通过三苄基化、醚化和三烯丙基化反应，成功地合成了磷侧二苄基配合物[{η 5-C5 H4（CH 2）2PMes-κ P}M（CH 2 Ph）2]（Zr-5，Hf-5）和磷侧二烯丙基配合物[{η5-C5 H4（CH 2）2PMes-κP}M（allyl）2]（Zr-7，Hf-7）. Zr-1和Hf-1经单三苯甲基化后与N-甲基咪唑反应，得到了含磷二氯化物配合物[{η5-C5 H4（CH 2）2PMes-κP} MCl 2（N-甲基咪唑）2]（Zr-13，Hf-13），并测定了Zr-13的晶体结构。此外，1当量Hf-1和2当量Hf-7之间的烯丙基氯交换反应也产生了不稳定的产物。
Synthesis of some Zr and Hf complexes with a phosphide-pendant cyclopentadienyl ligand was attempted via alkylation (tribenzylation, triallylation, or monotritylation) of the secondary phosphine-pendant trichloride complex [{η5-C5H4(CH2)2P(H)Mes-κP}MCl3(tht)] (Zr-1, Hf-1; Mes = 2,4,6-trimethylphenyl; tht = tetrahydrothiophene). The phosphide-pendant dibenzyl complex [{η5-C5H4(CH2)2PMes-κP}M(CH2Ph)2] (Zr-5, Hf-5) and the phosphide-pendant diallyl complex [{η5-C5H4(CH2)2PMes-κP}M(allyl)2] (Zr-7, Hf-7) were successfully prepared through tribenzylation followed by thermolysis and through triallylation, respectively, of Zr-1 or Hf-1. The phosphide-pendant dichloride complex [{η5-C5H4(CH2)2PMes-κP}MCl2(N-methylimidazole)2] (Zr-13, Hf-13) was also obtained through monotritylation of Zr-1 or Hf-1 followed by the treatment with N-methylimidazole, and the X-ray crystal structure of Zr-13 was determined. In addition, the allyl-chloride exchange reaction between 1 equiv of Hf-1 and 2 equiv of Hf-7 gave the unstable p...