New Reactions of Organmetallic Compounds

有机金属化合物的新反应

• 批准号: 11166221
• 负责人: OSAKADA Kohtaro
• 金额: $ 17.28万
• 依托单位: Tokyo Institute of Technology
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research on Priority Areas (A)
• 财政年份: 1999
• 资助国家: 日本
• 起止时间: 1999 至 2001
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-11166221/
• 关键词: Organometallic Complex; Theoretical Chemistry; Transition Metal; Ligand Transfer Reaction; Multinuclear Complex; 分子軌道計算; シリル配位子; 金属間結合; 白金; ロジウム; 理論計算; 有機遷移金属錯体; トランスメタル化; 複核錯体; d軌道

The reactions of transition metal complexes having M-Si a-bond were investigated both from experimental and theoretical views. Pt(SiHPh_2)_2(Pme_3)_2 undergoes thermal elimination of diphenylsilane to produce a new trinuclear Pt complex, [Pt(ヲフ-SiPh_2)(Pme_3)]_3. The molecular orbital calculation revealed that it is the first example of trinuclear complexes composed of Pt(0) centers and electron-releasing ligands. The reaction of dimethyl acetylenedicarboxylate (DMAD) with [Pt(ヲフ-SiPh_2)(Pme_3)]_3 leads to transformation of the framework to linear triplatinum clusters. Sila-3-platinacyclobutene was isolated from the reaction of Pt(SiHPh_2)_2(Pme_3)_2 with DMAD and characterized by X-ray crystallography. The formation pathway was found to involve ヲテ-Si-H bond activation of the 3-sila-1-propenylplatinum intermediate that is formed by the insertion of a DMAD into a Pt-Si bond of Pt(SiHPh_2)_2(Pme_3)_2. The results provided a new mechanism for the general reaction of alkyne with organosilane catalyzed by Pt ; the cylcization pathway with a low energy intermediate is more plausible than the classic mechanism that involves silylenoid intermediate with an extremely high energy.Rh and Ir complexes having halogeno (Cl, I) ligands and organosilyl ligands undergo coupling of these ligands to release the corresponding halosilanes. Dependence of the reaction rate on the structure of the complexes and on kind of the halogeno and silyl ligands revealed that the reaction involves intramolecular reductive elimination via concerted mechanism.In summary, the present study involving experimenetal and theoretical approach has revealed various aspects of reactions of organotransition metal complexes and elucidated the mechanism of several synthetic organic reactions that involve transmetalation as a crucial step.

从实验和理论两方面研究了含M-Si α键过渡金属配合物的反应。Pt（SiHPh_2）_2（Pme_3）_2与二苯基硅烷发生热消除反应，生成新的三核铂配合物[Pt（SiHPh_2）（Pme_3）]_3。分子轨道计算表明，这是第一个由Pt（0）中心和释电子配体组成的三核配合物。乙炔二甲酸二甲酯（DMAD）与[Pt（SiPh_2）（Pme_3）]_3的反应导致骨架转变为线性三铂簇合物。从Pt（SiHPh_2）_2（Pme_3）_2与DMAD的反应中分离得到了硅杂3-铂环丁烯，并用X-射线单晶衍射对其结构进行了表征。发现其形成途径涉及3-硅-1-丙烯基铂中间体（通过在Pt（SiHPh_2）_2（Pme_3）_2的Pt-Si键中插入DMAD而形成）的双金属-Si-H键活化。研究结果为Pt催化下炔与有机硅烷的一般反应提供了一种新的机理;低能中间体的环化途径比涉及极高能量的类硅烷基中间体的经典机理更合理;具有卤代（Cl，I）配体和有机硅烷基配体的Rh和Ir配合物通过这些配体的偶联释放出相应的卤代硅烷。反应速率与配合物结构、卤代配体和硅基配体种类的关系表明，该反应涉及分子内的还原消除反应.总之，本研究从实验和理论两方面揭示了有机过渡金属配合物反应的各个方面，并阐明了以金属转移反应为关键步骤的几种有机合成反应的机理.

项目成果

T.Yagyu, Y.Suzaki, K.Osakada: "Chemical Properties of Cationic Phenylplantium Complexes with a 2,2'-Bipyridine Ligand. Oxidative Addition of Mel, Insertion of Allene into the Pt-Ph Bond and Carbonylation"Organometallics. 21(in press). (2002)

T.Yagyu、Y.Suzaki、K.Osakada：“带有 2,2-联吡啶配体的阳离子苯基植物络合物的化学性质。梅尔的氧化加成、丙二烯插入 Pt-Ph 键和羰基化”有机金属化合物。

I.Yamaguchi, K.Osakada, T.Yamamoto, M.Katada: "1:2 Polycondensation of 3,3' -Diaminobenzidine and 1,1' -Ferrocenedimethan Catalyzed by RuCl_2(PPh_3)_3 to Afford Polybenzimidazole with Ferrocenylene Group"Bull. Chem. Soc. Jpn.. 72. 2257-2262 (1999)

I.Yamaguchi、K.Osakada、T.Yamamoto、M.Katada：“RuCl_2(PPh_3)_3 催化 3,3-二氨基联苯胺和 1,1-二茂铁二甲胺 1:2 缩聚生成二茂铁基聚苯并咪唑”Bull

T.Sakano, K.Osakada: "Polyacetylenes with Ferrocenophane Pendant Groups. Synthesis by Rh Complex Catalyzed Polyaddition, Chracterization, and the Properties"Macromol. Chem. Phys.. 202. 1829-1836 (2001)

T.Sakano、K.Osakada：“具有二茂铁侧基的聚乙炔。Rh 配合物催化加聚合成、表征和性能”Macromol。

Neli Mintcheva, Y.Nishihara, Atsunori Mori, K.Osakada: "Reaction of ArMe_2SiOH with cationic Pt-PPh_3 complexes. Si-C bond activation and formation of a siloxoplatinum complex"J. Organomet. Chem.. 629. 61-67 (2001)

Neli Mintcheva、Y.Nishihara、Atsunori Mori、K.Osakada：“ArMe_2SiOH 与阳离子 Pt-PPh_3 配合物的反应。Si-C 键活化和硅氧烷铂配合物的形成”J。

I.Yamaguchi, K.Miya, K.Osakada, T.Yamamoto: "Synthesis of Polyurea Rotaxanes Using a Cyclodextrin Complex of α,ω-Diamine"Polym. Bull.. 44. 247-253 (2000)

I.Yamaguchi、K.Miya、K.Osakada、T.Yamamoto：“使用 α,ω-二胺环糊精复合物合成聚脲轮烷”Polym. 44. 247-253 (2000)