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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. 用BX_3处理不同氨基取代亚磷酸盐的Cr、Mo、W配合物，形成具有M=P双键的阳离子配合物，该阳离子配合物随着亚磷酸盐配体氨基取代和螯合的增加以及中心金属原子序数的增加而稳定。过渡金属膦酸盐配合物的制备及其机理[Cp(CO)_2FeCl]与氨基取代亚磷酸盐的Arbuzov-like脱烷基反应得到阳离子配合物[Cp(CO)_2Fe[P(NR_2)Y(OR)]^+ (Y=OR,NR_2)，作为中间产物。它与Cl^-反应生成常规脱烷基产物[Cp(CO)_2Fe[P(O)(NR_2)Y]]，而与OR^-反应生成膦酸配合物[Cp(CO)_2Fe[P(0)Y(OR)]]，其中NR_2基团被选择性地消除。提出了一种合理的反应机理，即五配位金属磷烷与NR_2和进入的OR基团在轴向位置形成，然后OR基团被另一个OR^-攻击，释放出NR_2^-基团和醚r_2o。磷酸盐配体从中央向Cp环的迁移研究发现，当配合物经LDA处理后，磷酸盐配体P(0)RR‘定量迁移到[Cp(CO)LFe[P(O)RR’]]中的Cp环。用一些手性膦酸盐配合物考察了反应机理。过渡金属膦酸盐络合物的光化学反应在L （L=PPh_3或P(OR)_3）存在的情况下，用紫外线照射[Cp(CO)_2Fe[P(O)(OR)_2]]，形成一个CO基团被L取代的[Cp(CO)LFe[P(O)(OR)_2]]，而在没有L的情况下形成一个二聚体络合物，其中P=0基团取代CO。该反应被证明对合成有帮助。