Studies on the Chemistry of Platinum Group Element Complexes Relating to Catalysis

在这个由无机、生物无机和有机金属化学项目支持的项目中，罗切斯特大学的Richard Eisenberg博士将继续研究与均相催化和键激活有关的铂族元素配合物的化学。该项目的第一部分是继续进行涉及对氢诱导极化（PHIP）在新有机金属体系中的应用的机理研究。该方法可以检测新的氢化物中间体，并有助于阐明加氢的机理。通过氧化加入到各种金属中心的氢活化将被研究，包括铑和铱配合物能够在分子内C-H和C-C活化和钽二茂氢化物。本文还将研究烷基烷、烷基炔、亚胺和硫配合物中金属-非金属多键加成氢的过程，为四中心加成提供证据。PHIP将研究的催化反应包括不对称氢化和氢甲酰化。该项目的第二部分侧重于具有亲电性或自由基特征的有机金属系统的键激活和催化反应。将合成Ir（III）的阳离子二膦配合物和专门设计的四齿配体配合物。这些配合物将有两个相邻的不稳定位点用于底物结合、激活和偶联。铂和钯与新的二亚胺和二胺配体的相关亲电配合物也将被研究。这些和相关的配合物将在H/D交换、异构化、C-H键活化和烯烃聚合等反应中进行活性筛选。用含有四齿N和S给体的新型d7 Rh（II）和Ir（II）希夫碱配合物研究奇电子配合物的键激活。最广泛研究的金属反应是涉及甲烷、甲苯、烷烃和甲苯的碳氢活化反应，以及自由基驱动的聚合反应。开展铂族元素化合物与均相催化和键活化的化学研究项目。铂族元素配合物是当今工业中应用最广泛的催化剂，过去十年的发展，特别是不对称催化和聚合催化，表明这一作用将在未来增加。该计划将促进我们对金属发生的基本转变的理解，并将有助于为化学和制药工业设计新的重要催化剂。

In this project, which is supported by the Inorganic, Bioinorganic and Organometallic Chemistry program, Dr. Richard Eisenberg of the University of Rochester will continue his studies on the chemistry of platinum group element complexes relating to homogeneous catalysis and bond activation. Part one of the project is a continuation of mechanistic studies involving applications of parahydrogen induced polarization (PHIP) to new organometallic systems. This method can permit the detection of new hydride intermediates and may help elucidate the mechanism of hydrogen addition. The activation of hydrogen by oxidative addition to a variety of metal centers will be investigated, including rhodium and iridium complexes capable of intramolecular C-H and C-C activation and tantalocene hydrides. The addition of hydrogen to metal-nonmetal multiple bonds contained in alkylidene, alkylidyne, imido and sulfido complexes will also be studied in an effort to provide proof for a concerted 4-center addition. Catalytic reactions that will be investigated by PHIP include asymmetric hydrogenation and hydroformylation. Part two of the project focuses on the bond activation and catalytic reactions of organometallic systems that exhibit electrophilic or radical character. Cationic diphosphine complexes of Ir(III) and complexes with specifically designed tetradentate ligands will be synthesized. These complexes will have two adjacent labile sites for substrate binding, activation, and coupling. Related electrophilic complexes of Pt and Pd with new diimine and diamine ligands will also be studied. These and related complexes will be screened for reactivity in reactions that include H/D exchange, isomerizations, C-H bond activation, and olefin polymerizataion. Bond activation by odd electron complexes will be studied with new d7 Rh(II) and Ir(II) Schiff base complexes that contain tetradentate N and S donor ligands. The metalloradical reactions that will be studied most extensively are those involving C-H activation of methane, toluene, alkanes, and zylenes, and radical driven polymerizations. A program of research on the chemistry of platinum group element compounds relating to homogeneous catalysis and bond activation will be conducted. Platinum group element complexes include the most widely used catalysts in industry today, and developments in the past decade, particularly with regard to asymmetric catalysis and polymerization catalysis, suggest that this role will increase in the future. This program will advance our understanding of the fundamental transformations that take place at the metal and will help in the design of new important catalysts for the chemical and pharmaceutical industry.