Preparation of metallaphophinoheterocycle complexes and their reactivity attained by cooperative interaction of two metal centers with a substrate

金属磷杂环配合物的制备及其通过两个金属中心与底物的协同相互作用获得的反应性

• 批准号: 15550051
• 负责人: MIZUTA Tsutomu
• 金额: $ 2.43万
• 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: 2003
• 资助国家: 日本
• 起止时间: 2003 至 2004
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-15550051/
• 关键词: metallaphosphaheterocycle; [1]ferrocenophane; naphtho[1,8-b,c]phosphete; heterodinuclear complex; [1.1]ferrocenophane; metal insertion; palladium; platinum; パラダサイクル; ナフタレン; Heck反応触媒; W-Pdヘテロ2核錯体; スピロ架橋; ホスフィド架橋; リンヘテロ環; 歪み化合物; 挿入反応

Metallaphosphaheterocycle is a kind of metalloligand in which a metal-phosphorus covalent bond is incorporated in the ring. The ligand is expected to coordinate to a variety of metal centers through lone pair electrons on the phosphorus center to form heterodinuclear complexes in which two metal centers are located in close proximity.A platinum or palladium fragment was inserted into a phosphorus-carbon bond of phosphorus-bridged [1]ferrocenophane and naphtho[1,8-b,c]phosphete coordinating to a W(CO)_5 fragment. The metallaphosphaheterocycle thus formed was bonded to the W(CO)_5 fragment to form expected heterodinuclear framework. It was found that a ligand located between two metal centers of the dinuclear complex readily dissociates from the platinum or palladium center to form a vacant coordination site.A new phosphaheterocycle in which a PhP-PPh bond bridges 1,8-positions of naphthalene, 1,2-dihydro-1,2-diphenyl-naphtho[1,8-cd]-1,2-diphosphole (1), was prepared and used as a bridging ligand for the preparation of dinuclear group 6 metal complexes (OC)_5M(μ-1)M(CO)_5 (M=W(2a),Mo(2b),Cr(2c)).Photolysis of PPh-bridged [1]ferrocenophane (3)in ether gave PPh-bridged [1.1]ferrocenophane(4). After subsequent sulfurization of the reaction mixture with elemental sulfur, both syn and anti isomers of P(S)Ph-bridged [1.1]ferrocenophane (5)were successfully isolated and characterized by X-ray analysis. Upon heating, anti-3 isomerizes to syn-3, indicating thermodynamic stability of syn-3 over anti-3. A potential utility of syn-3 as a ligand was demonstrated by the formation of [CoCl_2(syn-2)](5)through a reaction of syn-3 with CoCl_2. The X-ray structure of 5 showed a novel chelate framework in which two phosphorus donor atoms are linked doubly with two ferrocene chelates.

金属磷杂环是一种金属配体，其环上含有金属磷共价键。该配体有望通过磷中心上的孤对电子与各种金属中心配合，形成两个金属中心靠近的异双核配合物。将铂或钯碎片插入磷桥接[1]二茂铁和萘[1,8-b，c]磷酸盐与W(CO)_5片段配位的磷-碳键中。由此形成的金属磷杂环与W(CO)_5片段结合形成预期的杂双核骨架。发现位于双核配合物两个金属中心之间的配体很容易与铂或钯中心解离，形成一个空的配位位。制备了一种新的磷杂环，其中PhP-PPh键桥接1,2-二氢-1,2-二苯基-萘[1,8-cd]-1,2-二磷孔(1)的1,8位，并作为桥接配体用于制备双核6族金属配合物（OC）_5M(μ-1)M(CO)_5 (M=W(2a),Mo（2b),Cr(2c)）。ph -桥接[1]二茂铁(3)在醚中光解得到ph -桥接[1.1]二茂铁(4)。随后用单质硫将反应混合物硫化后，成功分离出P(S) ph桥接[1.1]二茂铁(5)的同分异构体和反同分异构体，并通过x射线分析对其进行了表征。加热后，反-3异构成syn-3，表明syn-3相对于反-3具有热力学稳定性。syn3与CoCl_2反应生成[CoCl_2(syn2)](5)，证明了syn3作为配体的潜在效用。5的x射线结构显示出一种新的螯合框架，其中两个磷给体原子与两个二茂铁螯合物双重连接。

项目成果

Synthesis of a transition-metalated phosphinoborane dimer

• DOI: 10.1016/j.jorganchem.2004.04.024
• 发表时间: 2004-07
• 期刊: Journal of Organometallic Chemistry
• 影响因子: 2.3
• 作者: Kazuyuki Kubo;Ikue Kanemitsu;Eri Murakami;Tsutomu Mizuta;H. Nakazawa;K. Miyoshi

Synthesis and characterization of some zirconium and hafnium complexes with a phosphide-pendant cyclopentadienyl ligand

• DOI: 10.1021/om020916
• 发表时间: 2003-01
• 期刊: Organometallics
• 影响因子: 2.8
• 作者: T. Ishiyama;Tsutomu Mizuta;K. Miyoshi;H. Nakazawa

T.Ishiyama: "Synthesis and characterization of some zirconium and hafnium complexes with a phosphide-pendant cyclopentadienyl ligand"Organometallics. 22.5. 1096-1105 (2003)

T.Ishiyama：“具有磷化物侧挂环戊二烯基配体的一些锆和铪配合物的合成和表征”有机金属。