Bioorganometallic Catalysts: Strategies for Synthesis, Immobilization and Applications

这个奖项在无机，生物无机和有机化学计划支持研究教授Marcetta Y。Darensbourg在得克萨斯州A M大学追求一种新的范式，酶活性位点的建设来自酶乙酰辅酶A合成酶的活性位点，并开发NiN 2S 2和其他MN 2S 2复合物作为一类新的配体，支持有机金属化学。 基本的假设是，双核化妆的活性位点可以解释在金属二硫代酚作为配体的第二个，催化活性金属。通过这些衍生物的中性和阴离子NiN 2S 2金属配体的电子和空间特性是建立通过CO振动光谱和固态结构，分别。 通过对CO/烯烃共聚合反应（NiN_2S_2-Pd（II）（Me）_2）和加氢反应（NiN_2S_2-Rh（I）（CO）_2）的研究，阐明了Rh（I）和Pd（II）化合物C-C偶联催化过程中的基本有机金属反应。 其中一个目标是与Michael B教授合作，根据雅阁设计氢化酶模型复合物。Hall和测试了H2产生和H2活化的氢化酶样功能。 另一个目的是利用Ni（CGC）配合物的配位能力将反应性有机金属化合物锚在树脂珠上，以获得易于聚集和失活的反应性有机金属化合物的多相化和位点分离的优点。这项研究使用酶中复杂反应位点的合成模型来创造新的催化剂。 研究生将在无机/有机金属化学和生物学的接口工作，并参与指导和外展活动。

This award in the Inorganic, Bioinorganic and Organometallic Chemistry program supports research by Professor Marcetta Y. Darensbourg at Texas A&M University to pursue a new paradigm for enzyme active site construction derived from the active site of the enzyme Acetyl CoA Synthase and to develop NiN2S2 and other MN2S2 complexes as a new class of ligands that support organometallic chemistry. The basic hypothesis is that the binuclear makeup of the active sites may be interpreted in terms of metal-dithiolates as ligands to a second, catalytically active metal. Through these derivatives the electronic and steric characteristics of neutral and anionic NiN2S2 metalloligands are to be established via CO vibrational spectroscopy and solid state structures, respectively. Fundamental organometallic reactions in C-C coupling catalytic processes of the Rh(I) and Pd(II) compounds will be delineated through the study of reactions pertinent to CO/olefin co-polymerization (NiN2S2-Pd(II)(Me)2) and hydroformylation (NiN2S2-Rh(I)(CO)2). One aim focuses on hydrogenase model complexes designed in accord with computational studies in collaboration with Prof. Michael B. Hall and tested for hydrogenase-like function of H2 production and H2 activation. Another aim is to use the ligating ability of Ni(CGC) complex to anchor reactive organometallics on resin beads for the purpose of gaining the advantages of heterogenizing and site separation of reactive organometallics prone to aggregation and deactivation. This research uses synthetic models of complex reaction sites in enzymes to create new catalysts. Graduate students will work at the interface of inorganic/organometallic chemistry and biology and are also engaged in mentoring and out-reach activities.