Synthesis and Characterization of Some Zirconium and Hafnium Complexes with a Phosphide-Pendant Cyclopentadienyl Ligand
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- 作者：Takeshi Ishiyama ; Tsutomu Mizuta ; Katsuhiko Miyoshi ; and Hiroshi Nakazawa
- 刊名：Organometallics
- 出版年：2003
- 出版时间：March 3, 2003
- 年：2003
- 卷：22
- 期：5
- 页码：1096 - 1105
- 全文大小：208K
- 年卷期：v.22,no.5(March 3, 2003)
- ISSN：1520-6041
文摘
Synthesis of some Zr and Hf complexes with a phosphide-pendant cyclopentadienyl ligandwas attempted via alkylation (tribenzylation, triallylation, or monotritylation) of thesecondary phosphine-pendant trichloride complex [{
5-C5H4(CH2)2P(H)Mes-
P}MCl3(tht)] (Zr-1, Hf-1; Mes = 2,4,6-trimethylphenyl; tht = tetrahydrothiophene). The phosphide-pendantdibenzyl complex [{5-C5H4(CH2)2PMes-P}M(CH2Ph)2] (Zr-5, Hf-5) and the phosphide-pendant diallyl complex [{5-C5H4(CH2)2PMes-P}M(allyl)2] (Zr-7, Hf-7) were successfullyprepared through tribenzylation followed by thermolysis and through triallylation, respectively, of Zr-1 or Hf-1. The phosphide-pendant dichloride complex [{5-C5H4(CH2)2PMes-P}MCl2(N-methylimidazole)2] (Zr-13, Hf-13) was also obtained through monotritylation ofZr-1 or Hf-1 followed by the treatment with N-methylimidazole, and the X-ray crystalstructure of Zr-13 was determined. In addition, the allyl-chloride exchange reaction between1 equiv of Hf-1 and 2 equiv of Hf-7 gave the unstable phosphide-pendant monoallylmonochloride Hf complex [{5-C5H4(CH2)2PMes-P}HfCl(allyl)] (Hf-8), which was characterized as its derivatives [{5-C5H4(CH2)2PMes-P}Hf(Y)(allyl)] (Y = C6F5, Hf-14; Y = NPh2,Hf-15; Y = NEt2, Hf-16). It is proposed that the 3-alkyl-like ligand (benzyl, allyl, or trityl)in the secondary phosphine-pendant complex serves as an effective H-abstracting group togenerate the corresponding phosphide-pendant complex with liberation of the alkyl-Hcoupling product.
5-C5H4(CH2)2P(H)Mes-P}MCl3(tht)] (Zr-1, Hf-1; Mes = 2,4,6-trimethylphenyl; tht = tetrahydrothiophene). The phosphide-pendantdibenzyl complex [{5-C5H4(CH2)2PMes-P}M(CH2Ph)2] (Zr-5, Hf-5) and the phosphide-pendant diallyl complex [{5-C5H4(CH2)2PMes-P}M(allyl)2] (Zr-7, Hf-7) were successfullyprepared through tribenzylation followed by thermolysis and through triallylation, respectively, of Zr-1 or Hf-1. The phosphide-pendant dichloride complex [{5-C5H4(CH2)2PMes-P}MCl2(N-methylimidazole)2] (Zr-13, Hf-13) was also obtained through monotritylation ofZr-1 or Hf-1 followed by the treatment with N-methylimidazole, and the X-ray crystalstructure of Zr-13 was determined. In addition, the allyl-chloride exchange reaction between1 equiv of Hf-1 and 2 equiv of Hf-7 gave the unstable phosphide-pendant monoallylmonochloride Hf complex [{5-C5H4(CH2)2PMes-P}HfCl(allyl)] (Hf-8), which was characterized as its derivatives [{5-C5H4(CH2)2PMes-P}Hf(Y)(allyl)] (Y = C6F5, Hf-14; Y = NPh2,Hf-15; Y = NEt2, Hf-16). It is proposed that the 3-alkyl-like ligand (benzyl, allyl, or trityl)in the secondary phosphine-pendant complex serves as an effective H-abstracting group togenerate the corresponding phosphide-pendant complex with liberation of the alkyl-Hcoupling product.