Novel Bimetallic Complexes Based on Binucleating Polyphosphine Ligands

路易斯安那州立大学的George G. Stanley将在无机、生物无机和有机金属化学项目中研究双核多叔膦及其配位化合物的合成和化学反应性。我们将研究这些配位化合物在与烯烃的氢甲酰化反应中产生醛和随后的伯醇的催化行为，这两种反应都是商业上重要的有机化合物类别。Bisı苯基(2-diethylphosphinoethyl) phosphino !甲烷是一种四叔磷化氢，它与金属形成近距离的双金属配合物（闭合模式或“摇篮”配合物），以及一些四磷化氢类似物，将被用作本研究的选择配体。这组配体形成摇篮配合物的独特性质，而不是以前研究的聚膦通常观察到的开放模式，允许研究这一系列催化剂的金属协同性。要研究的反应包括共轭二烯（例如，丁二烯）的双氢甲酰化，前手性烯烃的不对称氢甲酰化，以及烯烃和炔环化和寡聚反应中的碳-碳键形成。

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.