Syntheses of reactive multinuclear metal complexes using various phosphorus ligands as a bridge

使用各种磷配体作为桥的反应性多核金属配合物的合成

基本信息

批准号：
15350035
负责人：
MIYOSHI Katsuhiko
金额：
$ 9.79万
依托单位：
Hiroshima University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
2003
资助国家：
日本
起止时间：
2003 至 2006
项目状态：
已结题

项目摘要

Dinuclear complexes have attracted continuous interest, since two metal centers in close proximity may provide a reaction site where both metals are engaged in multisite interactions with a substrate and/or consecutive activation and transformation of a substrate. In this project, novel phosphorus ligands were synthesized as a linker which can bridge two metal fragments having useful functionalities.Py-P-Fc Bridge. A phosphorus-bridged [1]ferrocenophane having a pyridine arm, Py-CH(Ph)-P(C_<10>H_8Fe) 1, was prepared as a precursor ligand. A tungsten complex having this strained phospha-heterocyle ligand, W(CO)_4(1), reacts with a Pd(PMe_3)_2 fragment to give a W-Pd complex(OC)_4W{μ-λN, P, C-PyCH(Ph)P(C_<10>H_8Fe)}Pd(PMe_3)_2 in which the Pd fragment inserts into a strained P-C bond. The complex was found to exhibit a selective ligand substitution at a coordination site where the two metal centers can interact simultaneously.P_2B_2 Bridge. An unprecedented aggregate of a transition-meta … More lated phosphinoborane was prepared. Cp(CO)_2Fe{P(BCl_3)HPh} was treated with n-BuLi to yield an iron-phosphinoborane dimer, μ-(PhPBCl_2)_2[Cp(C0)_2Fe]_2 2, via a dehydrohalogenation reaction. The X-ray structural study of 2 revealed that the dimer has a bent P_2B_2 4-membered ring.P-P Bridge. A bisphosphine in which a robust naphthalene group supports a P-P bond, 1,2-dihydro- 1,2-diphenyl-naphtho[1,8-c, d]1,2-diphosphole 3, was used as a bridging ligand for the preparation of dinuclear group 6 metal complexes. An M-P-P-M framework thus formed, μ-3-[W(C0)_5]_2, exhibited a thermal stability as expected.Cp-P-Cp Bridge. UV-Vis irradiation of P(=S)Ph-bridged [1]ferrocenophane, [Fe{(η^5-C_5H_4)_2P(=S)Ph}] in the presence of P(OMe)_3 gave a ring-slipped product, [Fe{(η^5-C_5H_4)(η^1-C_5H_4)P(=S)Ph}{P(OMe)_3 }_2] 4. When 4 having an,η^1-C_5H_4 group was allowed to react with [M(CO)_3(NCMe)_3] (M = Mo, W), iron-molybdenum and-tungsten heterodinuclear complexes μ{η^5, η^5-(C_5H_4)_2P(=S)Ph-kS}-[Fe{P(OMe)_3}_2][M(C0)_3] (M = Mo 5-Mo, W 5-W) were obtained, in which the two metal fragments were linked with an η^5-C_5H_4P(=S)Ph(η^5-C_5H_4)-kS bridge. In addition, 5-Mo and 5-W were readily converted in acetonitrile to the respective acetonitrile complexes μ-{ η^5,η^5-(C_5H_4)_2P(=S)Ph}-[Fe(NCMe){P(0Me)_3 }_2][M(C0)_3] with the P=S group giving up coordination to the iron center. Less

双核配合物引起了人们的持续关注，因为两个非常接近的金属中心可以提供一个反应位点，其中两种金属都参与与底物的多位点相互作用和/或底物的连续活化和转化。在该项目中，合成了新型磷配体。作为可以桥接两个具有有用功能的金属片段的连接体。Py-P-Fc桥具有吡啶臂的磷桥联的[1]二茂铁，制备Py-CH(Ph)-P(C_ 10 H_8Fe) 1 作为前体配体，具有该应变磷杂环配体W(CO)_4(1)的钨络合物与Pd(PMe_3)反应。 )_2 片段得到 W-Pd 复合物(OC)_4W{μ-λN, P, C-PyCH(Ph)P(C_ 10 H_8Fe)}Pd(PMe_3)_2，其中Pd片段插入紧张的P-C键中，发现该配合物在两种金属的配位位点上表现出选择性配体取代。中心可以同时相互作用。P_2B_2 桥。制备了一种前所未有的过渡元膦硼烷聚集体。用n-BuLi处理Cp(CO)_2Fe{P(BCl_3)HPh}，通过脱卤化氢反应得到铁-膦基硼烷二聚体μ-(PhPBCl_2)_2[Cp(C0)_2Fe]_2 2。 2的射线结构研究表明二聚体具有弯曲的P_2B_2 4元环。P-P桥是双膦。其中强大的萘基团支持 P-P 键，1,2-二氢- 1,2-二苯基-萘并[1,8-c, d]1,2-二膦 3 被用作桥连配体，用于制备由此形成的双核第6族金属配合物μ-3-[W(C0)_5]_2，显示出热稳定性： P(=S)Ph-桥联的[1]二茂铁，[Fe{(η^5-C_5H_4)_2P(=S)Ph}] 在 P 存在下的 Cp-P-Cp 桥。 (OMe)_3 得到环滑移产物， [Fe{(η^5-C_5H_4)(η^1-C_5H_4)P(=S)Ph}{P(OMe)_3 }_2] 4. 具有η^1-C_5H_4基团的4反应时与 [M(CO)_3(NCMe)_3] (M = Mo, W)，铁-钼-钨异双核配合物 μ{η^5，得到 η^5-(C_5H_4)_2P(=S)Ph-kS}-[Fe{P(OMe)_3}_2][M(C0)_3] (M = Mo 5-Mo, W 5-W) ，其中两个金属片段通过 η^5-C_5H_4P(=S)Ph(η^5-C_5H_4)-kS 桥连接。 5-Mo 和 5-W 在乙腈中很容易转化为各自的乙腈配合物 μ-{ η^5,η^5-(C_5H_4)_2P(=S)Ph}-[Fe(NCMe){P(0Me)_3 }_2][M(C0)_3]，P=S 组放弃与铁中心的协调。