Syntheses, structures, and reactivity of early transition metal complexes bearing a phosphide-donor multidentate ligand

研究了含膦侧链的环戊二烯及其锂盐的合成方法，即ER‘_3C5H4CH2CH2P(R)MES(ER’&lt；3&gt；=SimE_3，SnBu3；R=SimE_3H；MES=2，4，6-三甲基苯基)及其锂盐。考察了Cp衍生物与MCl4(M=Zr，Hf)的反应。结果表明，当R=SiMe_3时，生成了{C_5H_4CH_2CH_2P(SiMe_3)MeS}MCl3，膦部分不与中心金属配位。当R=H时，复杂反应工具的位置。相反，当以MCl4(Tht)^2为起始络合物(其中tht代表四氢噻吩环)时，磷化氢与中心金属配位形成了{C5H4CH2CH2P(H)Mes}mCl3(Tht)，考察了这些膦配合物向磷化物络合物的转化。三氯化物络合物没有转化为相应的磷化物络合物。接下来，尝试了氯/烷基交换反应。在R=H的情况下，与Mg(CH_2Ph)_2(THF)_2反应生成三苯基络合物。虽然膦部分不与中心金属配位，但该络合物在甲苯中热分解生成了释放甲苯的二苄基膦络合物。三氯化物与烯丙基格氏试剂在乙醚中反应生成棕色粉末状的二烯丙基磷化物络合物，考察了分离得到的磷化物-侧链络合物的反应性。与大体积醇2，6-二叔丁苯酚(HOR)的反应表明，在M-P键上发生O-H键加成反应生成非配位的膦-芳氧基配合物{C_5H_4CH_2CH_2P(H)Mes}M(C_3H_5)_2(OR)，然后去掉丙烯得到磷化物配位的配合物{C_5H_4CH_2CH_2PMes}M(C_3H_5)(OR)。

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).