Reactions of Metal-Metal-Bonded Binuclear Complexes

金属-金属键合双核配合物的反应

• 批准号: 59470036
• 负责人: NAKAMURA Yukio
• 金额: $ 4.61万
• 依托单位: Osaka City University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (B)
• 财政年份: 1984
• 资助国家: 日本
• 起止时间: 1984 至 1986
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-59470036/
• 关键词: Metal-Metal Bonds; Diphosphine Complexes; Model-Enzyme; Photochemical Reaction; Heterobinuclear Complexes; <mu> -Xylylene Complexes; μ-メチレン錯体

1. Reactions of M <(acac)_2> (M=Pd,Pt) with dppm(= <Ph_2> <PCH_2> <PPh_2> ) to from M <(dppm-H)_2> (dppm-H=a deprotonated dppm anion) and methylation of the carbanions in Pt <(dppm-H)_2> with MeI have been studied, and both the reaction schemes were elucidated with the aim of <^1H> , <^(13)C> , or <^(31)P> NMR spectroscopy.2. Reactions of <[Pd(dppm)_2]^(2+)> with <[CpMo(CO)_3]^-> as a nucleophile was examined to obtain a certain heterobimetallic complex and the desired complex [ <(CO)_3> Mo <((mu)-dppm)_2> -PdCp] ( <PF_6> ) was synthesized and characterized. 3. Photochemical reactions of <[CpMo(CO)_3]_2> with <NO(_2^-)> or dark reactions of <[CpMo(CO)_2]_2> with <NO(_2^-)> and <NO(_3^-)> have been elucidated to give the mononuclear complex [CpMo <(CO)_2> (NO)], and the reaction mechanism was also proposed.4. The nucleophilic attak of <[CpMo(CO)_3^-> at the benzyl carbons of <alpha> , <alpha> ' -dibromo-o, m, p-xylene was found to afford <mu> -xylylene complexes which react with <PMe_2> Ph to give acyl complexes. It was revealed that photo-irradiation of the <mu> -xylylene complexes induce homolytic cleavage of the Mo-C bond.5. The redox behavior of <[Rh(C_5Me_5)Me]_2> <(mu)-CH_2)_2> were examined by cyclic voltammetry and the presence of three oxidation waves were recognized. A possible scheme on the oxidation was proposed based on the following experimental data: controlled potential electrolysis, analysis of the evolved gases, and ESR measurement of the electrolyzed solution.

1.研究了M&lt；(Acac)_2&gt；(M=Pd，Pt；&lt；Ph_2&gt；&lt；Ph_2&gt；&lt；PPh_2&gt；)与M&lt；(dppm-H)_2&gt；(dppm-H=去质子化的dppm阴离子)与MeI的反应及碳负离子的甲基化反应。^(13)C&gt；或&lt；^(31)P&gt；核磁共振波谱。研究了亲核试剂&lt；[Pd(Dppm)_2]^(2+)&gt；与亲核试剂&lt；[CpMo(CO)_3]^-&gt；的反应，合成并表征了目标化合物[&lt；(CO)_3&gt；Mo&lt；((Mu)-dppm)_2&gt；-PdCp](&lt；PF_6&gt；)。3.阐明了&lt；[CpMo(CO)_3]_2&gt；与&lt；NO(_2^-)&gt；或&lt；[CpMo(CO)_2]_2&gt；与&lt；NO(_2^-)&gt；和&lt；NO(_3^-)&gt；的光化学反应，并提出了反应机理。~lt；[CpMo(CO)_3^-&gt；在&lt；α&gt；，&lt；α&gt；‘-二溴邻，m，对二甲苯的&lt；[CpMo(CO)_3^-&gt；]与&lt；PMe_2&gt；Ph反应生成了&lt；Mu&gt；-二甲苯配合物。结果表明，光照射引起了Mo-C键的均解断裂。用循环伏安法研究了~lt；[Rh(C_5Me_5)Me]_2&gt；&lt；(Mu)-CH_2)_2&gt；的氧化还原行为，发现存在三个氧化峰。基于以下实验数据，提出了一种可能的氧化方案：控制电位电解、析出气体分析和电解液的ESR测量。

项目成果

Hiromasa HASHIMOTO: "Novel Ligand Scrambling Reactions Caused by the Methylation and Protonation of the Carbanions in Bis(diphenylphosphino)methanido Complex of Platinum( <II> )." Bulletin of the Chemical Society of Japan.

Hiromasa HASHIMOTO：“铂（<II>）双（二苯基膦）亚氨基配合物中碳负离子的甲基化和质子化引起的新型配体扰乱反应。”

Kiyoshi ISOBE: "Photochemical Reactions of [ <Mo_2> <((eta)^5-C_5H_5)_2> <(CO)_6> ](Mo-Mo) and Dark Reactions of [ <Mo_2> <((eta)^5-C_5H_5)_2> <(CO)_4> ](Mo-Mo) with <NaNO_2> and <NaNO_3> : Reduction of <NO(_2^-)> and <NO(_3^-)> to Coordinated NO." Journa

Kiyoshi ISOBE：“[ <Mo_2> <((eta)^5-C_5H_5)_2> <(CO)_6> ](Mo-Mo) 的光化学反应和 [ <Mo_2> <((eta)^5”的暗反应

Hiromasa HASHIMOTO: "Reactions of Bis(beta-diketonato)platinum( <II> ) and -palladium( <II> ) with Diphosphines <Ph_2> <PCHRPPh_2> (R=H,Me) : Unexpected Formation of the Homoleptic Bis(diphenylphosphino)methanido and Related Complexes." Inorganica Chimica

Hiromasa HASHIMOTO：“双（β-二酮）铂（ <II> ）和-钯（ <II> ）与二膦 <Ph_2> <PCHRPPh_2> (R=H,Me) 的反应：均配双（二苯基膦）的意外形成

Kiyoshi ISOBE: Bulletin of the Chemical Society of Japan.

Kiyoshi ISOBE：日本化学会通报。

Hiromasa HASHIMOTO: "Consecutive Methylation and Protonation of the Carbanions in [Pt <(Ph_2PCHPPh_2)_2> ] Giving Rise to Ligand Scrambling." Inorganica Chimica Acta. 122. L9-L11 (1986)

Hiromasa HASHIMOTO：“[Pt <(Ph_2PCHPPh_2)_2> ] 中碳负离子的连续甲基化和质子化导致配体扰乱。”