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Preparation of Multinuclear Complexes by a Ring-Opening Reaction of a Highly Strained Cyclic Ferrocene Unit and Their Reactivity

高应变环状二茂铁单元开环反应制备多核配合物及其反应活性

基本信息

批准号：
13640560
负责人：
MIZUTA Tsutomu
金额：
$ 2.24万
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：
2001
资助国家：
日本
起止时间：
2001 至 2002
项目状态：
已结题

项目摘要

In this project, PhP-bridged [1] ferrocenophane (1) was utilized as a ligand having functionality for construction of multinuclear framework, because a single-atom-bridged [1] ferrocenophane readily undergoes a ring-opening reaction owing to its highly strained ring structure.When 1 or its sulfuriezed derivative is irradiated by UV-V is light in THF or CH_3CN, ring-opening polymerization takes place to give a polyferrocene derivative and trimers and dimers both of which have macrocyclic structures. A reaction mechanism was investigated for this ring-opening reaction, and was proposed as follows. 1), irradiation of 1 gives a ring-slipped product (2) in which one of the two Cp rings changes its coordination mode from n^5 to n^1. 2), the n^1-Cp of 2 attacks an iron center of another 2. 3), a ferrocene unit is reproduced and the n^1-Cp originally on the iron center of the letter 2 is expelled from the iron center. 4), a polyferrocene framework is propagated by repetition of the steps 1-3.A reaction of Pt(PMe_3)_4 with 1 coordinating to CpMn(CO)_2 and W(CO)_5 fragments gives heterodinuclear complexes (actually they are triangular complexes if an iron center of a ferrocene unit is included), in which a Pt(Pme_3)_2 fragment is inserted into a P-Cp bond of 1 to form P-Pt and N^1-C_5H_4-Pt bounds with a u-PPhFc bridge (u-PPhFc=u-PPh(C_5H_4FeC_5H_4)). X-ray analyses showed that the products are Cp(CO)_2Mn(u-PPhFc)Pt(Pme_3)_2 and(CO)_%W(uPPhFc)Pt(Pme_3)_2, respectively. Upon a similar reaction employing Pt(PPh_3)_4 in place of Pt(Pme_3)_4, CpMn(CO)\2(1) gives Cp(CO)Mn(u-CO)(u-PPhFc)Pt(PPh_3), whereas W(CO)_5(1) gives (CO)_4W(u-PPh_2)(u-PPh(C_5H_4FeC_5H_4H_4Ph))Pt(PPh_3), in which cleavage of a P-Ph bond of PPh_3 and migration of the Ph group to a ferrocene moiety take place.

PhP桥联的[1]二茂铁烷（1）是一种具有多核骨架功能的配体，由于单原子桥联的[1]二茂铁烷（1）具有高张力的环结构，容易发生开环反应，当1或其硫化衍生物在THF或CH_3CN中受到UV-Vis光照射时，发生开环聚合反应，得到聚二茂铁衍生物和均具有大环结构的三聚体和二聚体。研究了该开环反应的反应机理，并提出如下。1），照射1得到一个环滑移产物（2），其中两个Cp环之一将其配位模式从n^5变为n^1。2），2的n^1-Cp攻击另一个2的铁中心。3），一个二茂铁单元被再生，原来位于铁中心的n^1-Cp（字母2）被从铁中心排出。Pt（PMe_3）_4与1配位到CpMn（CO）_2和W（CO）_5上，得到异双核配合物（实际上，如果包括二茂铁单元的铁中心，则它们是三角形络合物），其中Pt（Pme_3）_2片段插入到1的P-Cp键中，形成P-Pt和N^1-C_5H_4-Pt键，并带有u-PPhFc桥（u-PPhFc=u-PPh（C_5H_4FeC_5H_4））。X射线衍射分析表明，产物分别为Cp（CO）_2Mn（u-PPhFc）Pt（Pme_3）_2和（CO）_%W（uPPhFc）Pt（Pme_3）_2。用Pt（PPh_3）_4代替Pt（Pme_3）_4进行类似的反应，CpMn（CO）_2（1）得到Cp（CO）Mn（u-CO）（u-PPhFc）Pt（PPh_3），而W（CO）_5（1）得到（CO）_4W（u-PPh_2）（u-PPh（C_5H_4FeC_5H_4H_4Ph））Pt（PPh_3），其中PPh_3的P-Ph键断裂，Ph基团迁移到二茂铁部分。