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

带有磷化物供体多齿配体的早期过渡金属配合物的合成、结构和反应性

• 批准号: 12640539
• 负责人: NAKAZAWA Hiroshi
• 金额: $ 2.3万
• 依托单位: Hiroshima University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2000
• 资助国家: 日本
• 起止时间: 2000 至 2001
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-12640539/
• 关键词: secondary phosphine complex; phosphide complex; group 4 transition metal; pendant ligand; diallyl complex; ホスフィン

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).

建立了带有膦侧基的环戊二烯ER'_3C_5H_4CH_2CH_2P(R)Mes (ER'_<3 >= SiMe_3, SnBu_3; R = SiMe_3 H; Mes = 2,4,6-三甲基苯基)及其Li盐的合成方法。研究了 Cp 衍生物与 MCl_4 (M = Zr, Hf) 的反应。发现当R=SiMe_3时,形成{C_5H_4CH_2CH_2P(SiMe_3)Mes}MCl_3且磷化氢部分不与中心金属配位。当R=H时，发生复杂的反应。相反，当使用MCl_4(tht)^2作为起始配合物（tht代表四氢噻吩）时，膦与中心金属配位形成{C_5H_4CH_2CH_2P(H)Mes}MCl_3(tht)。这些膦的转化检查了配合物进入磷化物配合物的情况。三氯化物络合物没有转化成相应的磷化物络合物。接下来，尝试Cl/烷基交换反应。当R=H时,与Mg(CH_2Ph)_2(thf)_2反应生成三苄基配合物。尽管膦部分不与中心金属配位，但该络合物在甲苯中的热解导致形成二苄基磷化物络合物并释放甲苯。三氯化物络合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。检查了分离的磷化物侧链络合物的反应性。与大体积醇 2,6-二叔丁基苯酚 (HOR) 的反应表明，O-H 键加成到 M-P 键上，生成膦不配位的芳氧基络合物 {C_5H_4CH_2CH_2P(H)Mes}M(C_3H_5)_2 ( OR)，然后消除丙烯，得到磷化物配位络合物{C_5H_4CH_2CH_2PMes}M(C_3H_5)(或)。

项目成果

H. Nakazawa: "Metallaphosphorane Chemistry : Preparations, Structures, and Reactivities"Bulletin of the Chemical Society of Japan. 74. 2255-2267 (2001)

H. Nakazawa：“金属正膦化学：制备、结构和反应性”日本化学会公报。

H. Nakazawa: "Conversion of a Stannyl-Phosphenium Complex into a Stannylene-Phosphine Complex of Mo and W : Double Bond Migration from M=P to M=Sn"Journal of Organometallic Chemisatry. 617. 453-463 (2001)

H. Nakazawa：“将甲锡烷基-磷络合物转化为 Mo 和 W 的甲锡烷基-膦络合物：从 M=P 到 M=Sn 的双键迁移”有机金属化学杂志。

K.Takano: "Ab Initio MO Study on Cationic Phosphenium Complexes of Group 6 transition Metals, fac- and mer-[(bpy)(CO)_3M{PN(Me)CH_2CH_2NMe}]^+(M=Mo,W)"Organometallics. 19・17. 3323-3331 (2000)

K.Takano：“第 6 族过渡金属阳离子磷配合物的从头 MO 研究，fac- 和 mer-[(bpy)(CO)_3M{PN(Me)CH_2CH_2NMe}]^+(M=Mo,W)”有机金属学. 19・17.

K. Kubo: "Syntheses and Crystal Structure of P-Transition-Metalated Iminophosphoranes, Cp*(CO)_2M {P(NPH)(OMe)_2} (M = Fe and Ru)"Organometallics. (in press). (2002)

K. Kubo：“P-过渡金属化亚氨基正膦的合成和晶体结构，Cp*(CO)_2M {P(NPH)(OMe)_2}（M = Fe 和 Ru）”有机金属化合物。

H.Nakazawa: "The Chemistry of Transition-Metal Complexes Containing a Phosphenium Ligand"Journal of Organometallic Chemistry. 611. 349-363 (2000)

H.Nakazawa：“含有磷配体的过渡金属配合物的化学”有机金属化学杂志。