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).

本文报道了含膦环戊二烯类化合物ER ′_3C_5H_4CH_2CH_2P（R）Mes（ER ′_<3 >= SiMe_3，SnBu_3; R = SiMe_3H; Mes = 2，4，6-三甲基苯基）及其锂盐的合成方法。考察了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，膦部分不与中心金属配位。当R = H时，复杂的反应发生。而以四氢噻吩为起始配位体的MCl_4（tht）^2则与中心金属配位生成{C_5H_4CH_2CH_2P（H）Mes}MCl_3（tht），并考察了这些膦配合物转化为膦配合物的过程。磷化物配合物没有转化为相应的磷化物配合物。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。虽然膦部分不与中心金属配位，但该配合物在甲苯中的热分解导致形成二苄基膦配合物，并释放甲苯。在乙醚中与烯丙基格氏试剂反应，生成棕色粉末状的二烯丙基磷化物，并对磷化物的反应活性进行了研究。与大体积醇2，6-二叔丁基苯酚（HOR）的反应表明，O-H键与M-P键发生加成反应，生成膦非配位芳氧基配合物{C_5H_4CH_2CH_2P（H）Mes}M（C_3H_5）_2（OR），然后丙烯发生消除反应，生成膦配位配合物{C_5H_4CH_2CH_2PMes}M（C_3H_5）（OR）。

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。

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.

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. 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。

K.Kubo: "Reduction of a CO Ligand in an Iron-Phosphonate Complex with a Neutral Borane Compound. Formation of a Formyl Complex with Intramolecular Coordination to a Boron Atom"Organometallics. 19・24. 4932-1934 (2000)

K.Kubo：“用中性硼烷化合物还原磷酸铁络合物中的CO配体。与硼原子进行分子内配位的甲酰基络合物的形成”有机金属学19・24（2000）。