Generation of Organometallic Conjugated Compounds Applicable for Non-linear Optics

适用于非线性光学的有机金属共轭化合物的生成

• 批准号: 10440207
• 负责人: MASHIMA Kazushi
• 金额: $ 8.13万
• 依托单位: Osaka University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B).
• 财政年份: 1998
• 资助国家: 日本
• 起止时间: 1998 至 2000
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-10440207/
• 关键词: Conjugation; Organometallic; Cluster; Molybdenum; Tantalum; Catalyst; Optical Property; Polymerization; 多核; 金属錯体; 工学特性; 非線形; パラジウム; ロジウム; 非線型

The construction of linear covalently-linked metal clusters has attracted much interest in view of fundamental bonding as well as promising applications as extensive electronic communications and optoelectronic materials. We have already reported synthesis and reaction of a linearly aligned tetranuclear complex, Mo_2Pd_2(pyphos)_4 (1)(pyphos=6-diphenylphosphino-2-prydonate), which was prepared by treating a quadruply bonded dinuclear dimolybdenum (II) complex, Mo_2(pyphos)_4 (2), with Pd_2(dba)_3(C_6H_6) in THF.The most interesting feature is that both Pd(O) atoms of 1 datively interacted with the Mo_2 core and hence the Pd(O) centers, unlike normal monoculear Pd(O) complexes, reacted oxidatively with dichloromethane at room temperature to give a Pd(II) complex, Mo_2PdCl_2(CH_2Cl)_2(pyphos)_4 (3). On monitoring the reaction of equation 1 by UV spectroscopy, the deep orange color (λ_<max>=476 nm) of 1 in dichloromethane turned immediately to greenish brown [the Pd(I) complex, Mo_2Pd_2Cl … More _2(pyphos)_4 (4) was deep green (λ_<max>=642 nm)], and then gradually resulted in the formation of the Pd(II) complex 3. We found that disulfides oxidatively added to both Pd(O) metals of 1 in a 1,4-addition reaction ; 1 reacted with one equivalent of diaryldisulfides in THF at room temperature to give the corresponding Pd(I)-thiolate complexes, Mo_2Pd_2(pyphos)_4(SAr)_2 (5a-f) in modest yields. Multiply-bonded tetranuclear complexes M_2Pd_2Cl_2(pyphos)_4 (6) and dinuclear complexes M_2(pyphos)_4 (7) (a, M=Mo ; b, M=Cr ; pyphos=6-diphenylphosphino-2-pyridonate) are found to exhibit large hyperpolarizability γ of nonlinear optical property by using the picosecond degenerate four-wave mixingg (DFWM) method ; the γ values of 6a (1.5×10^<-30> esu), 6b (5.2×10^<-31> esu), and 7a (6.9×10^<-31> esu) are greater than those (ca.10^<-35>-10^<-33> esu) of transition metal poly(yne) polymers.Recent development of the polymerization chemistry based on well-defined organometallic complexes is remarkable. Coordination polymerization of polar olefinic monomers such as methyl acrylate (MA) and methyl methacrylate (MMA) has been accomplished by using various enolate complexes. In this contribution, we would like to report the first Group 5 metal complex active for MMA polymerization. Moreover, we present our new idea to generate a catalytically active enolate complex from an organometallic complex bearing a polar monomer as a ligand. The coordinated MMA ligands of newly prepared tantalum complexes TaCp^*(η^2-p-MeOC_6H_4-DAD)(η^4supine-MMA)(8) (p-MeOC_6H_4-DAD=1,4-bis(p-methoxyphenyl)-1,4diaza-1,3-butadiene) and TaCp^*(η^2-Cy-DAD)(η^4-supine-MMA)(9) (Cy-DAD=1,4-dicyclohexyl-1,4-diaza-1,3-butadiene) were activated by addition of one equivalent of AlMe_3 to generate active catalysts for polymerization of MMA.The catalyst system of the highest activity was the combination of 9 and one equiv of AlMe_3 at -20℃ ; the polymerization completed within 10 min to give a PMMA with very narrow polydispersity (M_w/M_n=1.10). Less

鉴于基本键合以及作为广泛的电子通信和光电合成材料的有前景的应用，线性共价连接的金属簇的构建引起了人们的极大兴趣，我们已经报道了线性排列的四核配合物Mo_2Pd_2(pyphos)_4的反应。 (1)(pyphos=6-二苯基膦-2-prydonate)，通过处理四键双核制备二钼 (II) 络合物，Mo_2(pyphos)_4 (2)，与 Pd_2(dba)_3(C_6H_6) 在 THF 中。最有趣的特征是 1 的两个 Pd(O) 原子与 Mo_2 核发生配位相互作用，因此与普通单核 Pd(O) 配合物不同，Pd(O) 中心在室温下与二氯甲烷发生氧化反应，产生Pd(II) 络合物，Mo_2PdCl_2(CH_2Cl)_2(pyphos)_4 (3) 通过紫外光谱监测方程式 1 的反应，二氯甲烷中 1 的深橙色 (λ_<max>=476 nm) 立即变成 。绿棕色 [Pd(I) 络合物，Mo_2Pd_2Cl … 更多 _2(pyphos)_4 (4) 呈深绿色(λ_<max>=642 nm)]，然后逐渐形成Pd(II)络合物3。我们发现，在1,4-加成反应中，二硫化物氧化加成到1的两种Pd(O)金属上；1与一当量的二芳基二硫化物在THF中在室温下反应得到相应的Pd(I)-硫醇络合物， Mo_2Pd_2(pyphos)_4(SAr)_2 (5a-f) 产率适中的多重键合四核配合物 M_2Pd_2Cl_2(pyphos)_4 (6) 和双核配合物 M_2(pyphos)_4 (7) (a, M=Mo; b) ，M=Cr ；pyphos=6-二苯基膦-2-吡啶酮酸酯）利用皮秒简并四波混频（DFWM）方法表现出大的超极化率γ的非线性光学特性；6a（1.5×10^<-30> esu）、6b（5.2×10^<-）的γ值； 31> esu) 和 7a (6.9×10^<-31> esu) 大于这些(ca.10^<-35>-10^<-33> esu) 过渡金属聚(炔)聚合物。基于明确的有机金属配合物的聚合化学的最新发展是引人注目的。由于丙烯酸甲酯（MA）和甲基丙烯酸甲酯（MMA）是通过使用各种烯醇化物配合物来实现的，在这篇文章中，我们想报告第一组。此外，我们提出了从带有极性单体作为配体的有机金属配合物生成催化活性烯醇配合物的新想法。 -p-MeOC_6H_4-DAD)(η^4仰卧-MMA)(8) (p-MeOC_6H_4-DAD=1,4​​-双(对甲氧基苯基)-1,4二氮杂-1,3-丁二烯) 和 TaCp^*(η^2-Cy-DAD)(η^4-仰卧-MMA) (9) (Cy-DAD=1,4​​-二环己基-1,4-二氮杂-1,3-丁二烯)通过添加一当量的AlMe_3进行活化生成用于MMA聚合的活性催化剂。最高活性的催化剂体系是9和1当量的AlMe_3的组合，在-20℃下聚合在10分钟内完成，得到具有很窄的多分散性的PMMA（M_w/M_n= 1.10).更少

项目成果

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