Bioorganometallic Catalysts: Strategies for Synthesis, Immobilization and Applications

生物有机金属催化剂：合成、固定化和应用策略

• 批准号: 0616695
• 负责人: Marcetta Darensbourg
• 金额: $ 54.6万
• 依托单位: Texas A&M Research Foundation
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2006
• 资助国家: 美国
• 起止时间: 2006-09-01 至 2009-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0616695&HistoricalAwards=false
• 关键词: Bioorganometallic; Catalysts; Strategies; Synthesis; Immobilization

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.

该奖项在无机，生物促和有机金属化学计划中支持德克萨斯州A＆M大学的Marcetta Y. Darensbourg教授的研究，以追求一种新的范围，以源自酶的活性场所构建，该范围源自酶的乙酰乙酰基CoA合成酶的活性地点，并开发了Nin2S2S2和其他NIN2S2S2S2和其他MN2S2复合物作为支持有机化学的新的配体。 基本的假设是，活性位点的双核构成可以用金属 - 二硫代元素解释为二秒，催化活性金属的配体。通过这些衍生物，将分别通过CO振动光谱和固态结构建立中性和阴离子NIN2S2金属素的电子和空间特性。 RH（I）和PD（II）化合物的C-C耦合催化过程中的基本有机金属反应将通过研究与CO/Olefin共聚合（NIN2S2S2S2S2-PD（II）2）和加氢甲基化的反应研究来划定（NIN2S2-RH（i）（CO）2）。 一个目标重点是与迈克尔·B·霍尔教授合作设计的氢化酶模型复合物，并测试了H2生产和H2激活的氢化酶样功能。 另一个目的是利用Ni（CGC）复合物的连接能力锚定在树脂珠上的反应性有机金属，以获得异质化和位点分离的优势，使反应性有机金属分离容易聚集和失活。该研究使用酶中复杂反应位点的合成模型来创建新的催化剂。 研究生将在无机/有机金属化学和生物学的界面上工作，还从事指导和范围的活动。