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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

双核配合物已经吸引了持续的兴趣，因为两个金属中心非常接近可以提供反应位点，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。在本项目中，合成了新型的磷配体作为连接基团，其可以桥接具有有用功能的两个金属片段。Py-P-Fc Bridge。合成了一种含吡啶臂的磷桥[1]二茂铁并菲（Py-CH（Ph）-P（C_<10>H_8Fe）_1）作为前体配体。具有这种张力磷杂环配体的钨配合物W（CO）_4（1）与Pd（PMe_3）_2片段反应得到W-Pd配合物（OC）_4W{μ-λN，P，C-PyCH（Ph）P（C_<10>H_8Fe）}Pd（PMe_3）_2，其中Pd片段插入张力P-C键。发现该配合物在两个金属中心可以发生相互作用的配位点上表现出选择性的配体取代。一个前所未有的过渡元聚合 ...更多信息制备了取代的膦基硼烷。Cp（CO）_2Fe{P（BCl_3）HPh}与正丁基锂发生脱卤化氢反应，生成铁膦硼烷二聚体μ-（PhPBCl_2）_2[Cp（CO）_2Fe]_22。X-射线结构分析表明，二聚体中含有一个弯曲的P_2B_2四元环。以1，2-二氢-1，2-二苯基萘并[1，8-c，d] 1，2-二磷杂环戊烯-3为桥联配体，合成了双核第6族金属配合物。由此形成的M-P-P-M骨架μ-3-[W（C 0）_5]_2具有预期的热稳定性。在P（OMe）_3存在下，P（=S）Ph桥联的[1]二茂铁番[Fe{（η^5-C_5H_4）_2P（=S）Ph}]经紫外-可见光照射，得到一个开环产物[Fe{（η^5-C_5H_4）（η^1-C_5H_4）P（=S）Ph}{P（OMe）_3 }_2] 4。当4带有η^1-C_5H_4基团时，可与[M（CO）_3（NCMe）_3]反应（M = Mo、W），铁钼钨异双核配合物μ{η^5，η^5-（C_5H_4）_2P（=S）Ph-kS}-[Fe{P（OMe）_3}_2][M（C 0）_3]（M = Mo 5-Mo，W5-W），其中两个金属碎片通过η^5-C5 H4 P（=S）Ph（η^5-C5 H4）-kS桥连接。此外，5-Mo和5-W在乙腈中容易地转化为相应的乙腈配合物μ-{ η^5，η^5-（C_5H_4）_2P（=S）Ph}-[Fe（NCMe）{P（OMe）_3 }_2][M（CO）_3]，其中P=S基团放弃与铁中心的配位。少