Preparation and Reactivity of Organometallic Complexes with Phosphorus Compounds as Covalent Ligands

以磷化合物为共价配体的有机金属配合物的制备及其反应活性

基本信息

批准号：
01470052
负责人：
MIYOSHI Katsuhiko
金额：
$ 0.26万
依托单位：
Heroshima University
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (B)
财政年份：
1989
资助国家：
日本
起止时间：
1989 至 1990
项目状态：
已结题

项目摘要

1. Preparation and Reactivity of Transition-metal Complexes Having a Multiple Bond to the PhosphorusTreatment of Cr, Mo, and W complexes of various amino-substituted phosphites with BX_3 led to the formation of the cationic complexes with an M=P double bond, which are stabilized with increase in the amino-substitution and in chelation of the phosphite ligands and with the atomic number of the central metals.2. Preparation of Transition-metal Phosphonate Complexes and the MechanismThe Arbuzov-like dealkylation reaction of [Cp(CO)_2FeCl] with amino-substituted phosphites gave a cationic complex [Cp(CO)_2Fe[P(NR_2)Y(OR)]^+ (Y=OR,NR_2), which is regarded as an intermediate. The reaction of it with Cl^- yielded usual dealkylation products[Cp(CO)_2Fe[P(O)(NR_2)Y]], While the treatment with OR^- afforded a phosphonate complex [Cp(CO)_2Fe[P(0)Y(OR)]] where the NR_2 group is selectively eliminated. A plausible reaction mechanism is proposed in which a pentacoordinate metallaphosphorane is once formed with the NR_2 and incoming OR groups in axial positions, and then the OR group is attacked by another OR^- to release to release the NR_2^- group and the ether R_2O.3. Migration of the Phosphonate Ligand from the Central to the Cp RingThe phosphonate ligand P(0)RR' is found to migrate quantitatively to the Cp ring in [Cp(CO)LFe[P(O)RR']] when the complex is treated with LDA. The reaction mechanism was examined by use of some chiral phosphonate complexes.4. Photo-chemical Reaction of Transition-metal Phosphonate ComplexesWhen the [Cp(CO)_2Fe[P(O)(OR)_2]] is irradiated with UV in the presence of L (L=PPh_3 or P(OR)_3), [Cp(CO)LFe[P(O)(OR)_2]] is formed with one CO group replaced by L, whereas a dimeric complex is formed in the absence of L, in which the P=0 group is coordinated in place of CO. The reaction was proved useful for synthetic purposes.

1。与具有BX_3的各种氨基氨基磷酸化磷酸盐的Cr，MO和W复合物多重键合的过渡金属复合物的制备和反应性，导致阳离子复合物形成M = P双键，它们在氨基 - 固定型和磷酸化层中的氨基化型和磷酸化的数量上的增加而稳定，并且在磷酸化的层次中的数量增加。 Preparation of Transition-metal Phosphonate Complexes and the MechanismThe Arbuzov-like dealkylation reaction of [Cp(CO)_2FeCl] with amino-substituted phosphites gave a cationic complex [Cp(CO)_2Fe[P(NR_2)Y(OR)]^+ (Y=OR,NR_2), which is regarded as an intermediate.它与Cl^的反应产生了常规的脱甲基化产物[CP（CO）_2FE [P（o）（NR_2）Y]]，而使用OR^的处理获得了磷酸化合物复合物[CP（CO）_2FE [P（0）Y（OR）]，其中NR_2组选择性地消除了。提出了一种合理的反应机制，其中曾经用NR_2形成了五角座的元磷酸酯，并在轴向位置形成或组，然后由另一个或^ - 释放或组释放NR_2^ - 组和Ether R_2O.3。磷酸配体从中心向CP迁移磷酸配体P（0）rr'当用LDA处理复合物时，在[CP（CO）LFE [P（o）RR']]中定量迁移至CP环。通过使用一些手性磷酸复合物检查反应机理4。当[cp（co）_2fe [p（o）（OR）_2]] [cp（co）_2fe [p（o）（OR）_2]]在L（L = PPH_3或P（OR P（OR）_3）存在下，将紫外线照射[Cp（co）_2FE [p（o）（OR）_2]]的光化学反应会被辐射没有L的不存在，其中P = 0组由CO协调。事实证明，该反应可用于合成目的。