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.

无机化学、生物无机化学和金属有机化学项目的这一奖项支持了德克萨斯农工大学Marcetta Y.Darensburg教授的研究，他致力于利用乙酰辅酶A合成酶的活性位点构建酶活性位点的新范例，并将NiN2S2和其他MN2S2络合物开发为支持有机金属化学的新型配体。基本假设是，活性中心的双核组成可以用金属--二硫代硫酸盐作为第二个催化活性金属的配体来解释。通过这些衍生物，分别通过CO振动光谱和固态结构确定了中性和阴离子NiN_2S_2金属配体的电子和空间性质。通过对CO/烯烃共聚反应(NiN2S2-Pd(II)(Me)2)和氢甲酰化反应(NiN2S2-Rh(I)(CO)2)的研究，描述了Rh(I)和Pd(II)化合物C-C耦合催化过程中的基本有机金属反应。一个目标是与Michael B.Hall教授合作设计符合计算研究的氢酶模型复合体，并测试氢酶样产氢和氢气活化功能。另一个目的是利用镍(CGC)络合物的连接能力将活性金属固定在树脂珠上，以获得易聚集和失活的活性金属的异相和位置分离的优势。这项研究使用酶中复杂反应部位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界面上工作，还将参与指导和外展活动。