Specific Chemical Conversion Based on the Cooperative Effect of Two Transition Metal Fragments in Close Proximity

基于两种邻近过渡金属片段协同作用的特定化学转化

• 批准号: 09440245
• 负责人: TOBITA Hiromi
• 金额: $ 8.06万
• 依托单位: TOHOKU UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 1997
• 资助国家: 日本
• 起止时间: 1997 至 1999
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-09440245/
• 关键词: BRIDGED SILYLENE COMPLEX; PHOTOREACTION; BRIDGED PHOSPHIDO COMPLEX; ALKYNE; C-C BOND FORMATION; DISULFIDO LIGAND; IRON COMPLEX; RETHENIUM COMPLEX; クラスター合成; トリスルフィド配位子; 動的挙動; シリル錯体; アーレン錯体; シリレン錯体; ホスフィド錯体; 二核錯体; ヒドロシラン; 再分配反応; シリリン錯体; ベ

(1) Irradiation of CpFe(CO)ィイD22ィエD2SiMeィイD23ィエD2 in the presence of trihydrosilane RィイD22ィエD2CHSiHィイD23ィエD2 (R = Et, Ph) afforded a silylene-bridged dinuclear complex CpィイD22ィエD2(CO)ィイD22ィエD2FeィイD22ィエD2(μ-CO){μ-Si(H)CHRィイD22ィエD2} (R = Et, Ph). On the other hand, irradiation of Cp*Fe(CO)ィイD22ィエD2SiMeィイD23ィエD2, which has bulky Cp* ligand, in the presence of PhィイD22ィエD2CHSiHィイD23ィエD2 gave a mononuclear complex Cp*Fe(CO)ィイD22ィエD2{Si(H)ィイD22ィエD2CHPhィイD22ィエD2} as a main product. By photoreaction of this mononuclear complex with CpFe(CO)ィイD22ィエD2SiMeィイD23ィエD2 or CpW(CO)ィイD23ィエD2Me, we succeeded in the selective synthesis of unsymmetrical silylene-bridge iron-iron and iron-tungsten complexes Cp*(CO)Fe(μ-CO){μ-Si(H)CHPhィイD22ィエD2}(CO)ィイD2nィエD2MCp (M = Fe, n = 1 ; M = W, n = 2). This reaction could become a general method of the synthesis of unsymmetrical silylene-bridged complexes which is rare.(2) Reactions of phosphido-bridged iron-iron and iron-ruthenium complexes with various alkynes were investigated. As a result, the iron-iron complexes yielded several types of complexes in which one or two molecules of alkynes were coupled with a carbonyl ligand and a phosphido ligand to form a bridging ligand that bridged two iron atoms. The product type changed depending on the alkyne, metal center, and supporting ligands. On the other hand, the iron-ruthenium complexes provided the products in which only an alkyne and a carbonyl ligand were coupled and bridged the iron and ruthenium atoms. These seem to be new types of carbon-carbon and carbon-phosphorus bond formation reactions. Their reaction mechanisms are currently under investigation.(3) Using disulfido-bridged diiron complexes as precursors, several new types of sulfur-bridged clusters containing metal cores of FeィイD22ィエD2Ru, FeィイD22ィエD2RuィイD22ィエD2, FeィイD22ィエD2Cr, FeィイD22ィエD2W, etc. were synthesized and the structures and fluxional behaviors of them were clarified.

(1)在三氢硅烷R D22 D2CHSiH D23 D2（R = Et，Ph）存在下，照射CpFe（CO）D22 D2 SiMe D23 D2，得到了一个硅撑桥联双核配合物Cp D22 D2（CO）D22 D2 Fe D22 D2（μ-CO）{μ-Si（H）D22 D2}（R = Et，Ph）.另一方面，具有大体积Cp* 配体的Cp*Fe（CO）D22 D2 SiMe D2在Ph D22 D23 D2的存在下照射，得到单核配合物Cp*Fe（CO）D22 D2{Si（H）D22 D2CHPh D22 D2}作为主要产物。通过该单核配合物与CpFe（CO）D22 D2 SiMe D23 D2或CpW（CO）D23 D2 Me的光反应，成功地选择性合成了不对称硅桥铁-铁和铁-钨配合物Cp*（CO）Fe（μ-CO）{μ-Si（H）CHPh D22 D2}（CO）D2 n D2 MCp（M = Fe，n = 1 ; M = W，n = 2）.该反应有望成为合成不对称硅桥配合物的一种通用方法。(2)研究了磷桥联铁-铁和铁-钌配合物与各种炔的反应。结果，铁-铁络合物产生了几种类型的络合物，其中一个或两个分子的炔与羰基配体和膦配体偶联，形成桥接两个铁原子的桥接配体。产物类型根据炔、金属中心和支持配体而变化。另一方面，铁-钌配合物提供的产物中，只有一个炔和一个羰基配体耦合和桥接的铁和钌原子。这些似乎是新型的碳-碳和碳-磷键形成反应。其反应机理目前正在研究中。(3)以二硫键桥联的二铁配合物为前驱体，合成了以Fe_（22）O_（22）Ru_（22）O_（22）Cr_（22）O_（22）W_（22）O_（22

项目成果

陸 龍翔: "Preparation of Silanediyl-Bridged Fe-Fe and Fe-W Dinuclear Complexes.X-Ray Structures of[Cp^*Fe(CO)(μ-CO){μ-Si(H)CHPh_2}(CO)_nMCp]・・・" Bull.Chem.Soc.Jpn.71・12. 2865-2871 (1998)

鲁龙翔：“硅烷二基桥联Fe-Fe和Fe-W双核配合物的制备。[Cp^*Fe(CO)(μ-CO){μ-Si(H)CHPh_2}(CO)的X射线结构” _nMCp]...”Bull.Chem.Soc.Jpn.71・12.2865-2871 (1998)

飛田 博実: "Synthesis of Cationic Germyleneiron Complexes and X-ray Structure of[Cp^*(CO)_2Fe=GeMe_2・DMAP]BPh_4・CH_3CN(Cp^*=C_5Me_5,DMAP=・・・" Organometallics. 17・5. 789-794 (1998)

Hiromi Tobita：“[Cp^*(CO)_2Fe=GeMe_2・DMAP]BPh_4・CH_3CN(Cp^*=C_5Me_5,DMAP=...的阳离子甲锗烷铁配合物的合成和X射线结构”有机金属学。17・5。 789-794 (1998)

荻野博: "Bridged silylene and germylene complexes"Adv.Organomet.Chem.. 42巻. 223-290 (1998)

Hiroshi Ogino：“桥连亚甲硅基和甲亚甲亚甲基配合物”Adv.Organomet.Chem.. vol. 42. 223-290 (1998)

Lung-Shiang Luh, Yuh-Sheng Wen, Hiromi Tobita, and Hiroshi Ogino: "Preparation of silanediyl-bridged Fe-Fe and Fe-W dinuclear complexes. X-ray structure of [Cp*Fe(CO)(μ-CO){μ-Si(H)CHPhィイD22ィエD2}(CO)ィイD2nィエD2MCp] (Cp* = CィイD25ィエD2MeィイD25ィエD2, Cp = CィイD25ィエ

Lung-Shiang Luh、Yuh-Sheng Wen、Hiromi Tobita 和 Hiroshi Ogino：“硅烷二基桥联的 Fe-Fe 和 Fe-W 双核配合物的制备。[Cp*Fe(CO)(μ-CO) 的 X 射线结构” {μ-Si(H)CHPh D22D2}(CO)D2nD2MCp] (Cp* = CD25D2MeD25D2, Cp = CD25 工人

和田 裕明: "Intramolecular Aromatic C-H Bond Activation by a Silylene Ligand in a Methoxy-Bridged Bis (silylene)-Ruthenium Complex" Organometallics. 16・18. 3870-3872 (1997)

Hiroaki Wada：“甲氧基桥双（亚硅基）-钌络合物中的亚硅基配体的分子内芳香族 C-H 键活化”有机金属学 16・18（1997）。