| Budget Amount *help |
¥3,600,000 (Direct Cost: ¥3,600,000)
Fiscal Year 2001: ¥1,400,000 (Direct Cost: ¥1,400,000)
Fiscal Year 2000: ¥2,200,000 (Direct Cost: ¥2,200,000)
|
|---|
| Research Abstract |
Synthetic methods of cyclopentadienes with a phosphine pendant, ER'_3C_5H_4CH_2CH_2P(R)Mes (ER'_<3 >= SiMe_3, SnBu_3; R = SiMe_3 H; Mes = 2,4,6-trimethylphenyl) and their Li salts were developed. The reactions of the Cp derivatives with MCl_4 (M = Zr, Hf) were examined. It was found that when R = SiMe_3, {C_5H_4CH_2CH_2P(SiMe_3)Mes}MCl_3 is formed and the phosphine portion does not coordinate to the central metal. When R = H, the complicated reactions tool place. In contrast, when MCl_4(tht)^2 was used as a starting complex where tht stands for tetrahydrothiophene, {C_5H_4CH_2CH_2P(H)Mes}MCl_3(tht) was formed with coordination of the phosphine to the central metal.
The conversion of these phosphine complexes into the phosphide complexes was examined. The trichloride complexes were not converted into the corresponding phosphide complexes. Next, a Cl/alkyl exchange reaction was attempted. In the case of R = H, a tribenzyl complex was formed in the reaction with Mg(CH_2Ph)_2(thf)_2. Although the phosphine part does not coordinate to the central metal the thermolysis of this complex in toluene led to the formation of a dibenzylphosphide complex with releasing toluene. The reaction of the trichloride complex with an allyl Grignard reagent in ether yielded a diallylphosphide complex as a brown powder.
The reactivity of the isolated phosphide-pendant complex was examined. The reaction with bulky alcohol, 2,6-ditertiaryBu-phenol (HOR), revealed that the O-H bond addition to the M-P bond takes place to give a phosphine-uncoordinated aryloxy complex {C_5H_4CH_2CH_2P(H)Mes}M(C_3H_5)_2 (OR), followed by the elimination of propene to give a phosphide-coordinated complex {C_5H_4CH_2CH_2PMes}M(C_3H_5)(OR).
|
