Novel Bimetallic Complexes Based on Binucleating Polyphosphine Ligands

基于双核多膦配体的新型双金属配合物

• 批准号: 8823041
• 负责人: George Stanley
• 金额: $ 20.22万
• 依托单位: Louisiana State University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 1989
• 资助国家: 美国
• 起止时间: 1989-03-01 至 1992-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=8823041&HistoricalAwards=false
• 关键词: Novel; Bimetallic; Complexes; Based; Binucleating

George G. Stanley of Louisiana State University will study the synthesis and chemical reactivity of binucleating polytertiary- phosphines and their coordination compounds in this research within the Inorganic, Bioinorganic and Organometallic Chemistry Program. These coordination compounds will be examined with respect to their catalytic behavior on the hydroformylation reaction with alkenes to produce aldehydes and subsequently primary alcohols, both of which are commercially important classes of organic compounds. Bisıphenyl(2-diethylphosphinoethyl)phosphino!methane, a tetra- tertiary phosphine which forms bimetallic complexes with the metals in close proximity (closed-mode or "cradle" complexes), and some tetraphosphine analogues, will be used as the ligands of choice for this study. The unique property of this set of ligands to form the cradle complexes, instead of the open-mode usually observed with previously examined polyphosphines, allows the study of metal cooperativity in this series of catalysts. Reactions to be studied include double hydroformylation of conjugated dienes (e.g., butadiene), asymmetric hydro-formylation of prochiral alkenes, and carbon-carbon bond formation in alkene and alkyne cyclizations and oligomerizations.

路易斯安那州立大学的乔治·G·斯坦利将在无机、生物无机和有机金属化学计划的这项研究中研究双核多叔膦及其配位化合物的合成和化学反应活性。将考察这些配位化合物在与烯烃的氢甲酰化反应中的催化行为，以生成醛和伯醇，这两类化合物都是商业上重要的有机化合物。Bisıphenyl(2-diethylphosphinoethyl)phosphino！methane，是一种四叔基膦，它与近邻的金属形成双金属络合物(闭式或“摇篮”络合物)，以及一些四膦类似物，将被用作本研究的首选配体。这组配体形成摇篮络合物的独特性质，而不是以前研究过的多膦配体通常观察到的开放模式，使我们能够研究这一系列催化剂中的金属协同性。要研究的反应包括共轭双烯(如丁二烯)的双氢甲酰化，前手性烯烃的不对称氢甲酰化，以及在烯烃和烯烃中形成碳-碳键的环化和齐聚反应。