Synthetic Studies in Homogeneous Catalysis and Organometallic Chemistry

均相催化和有机金属化学的合成研究

• 批准号: 0131206
• 负责人: James Collman
• 金额: $ 93.5万
• 依托单位: Stanford University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2002
• 资助国家: 美国
• 起止时间: 2002-02-01 至 2005-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0131206&HistoricalAwards=false
• 关键词: Synthetic; Studies; Homogeneous; Catalysis; Organometallic

James Collman of Stanford University is supported by the Inorganic, Bioinorganic, and Organometallic Chemistry Program for research on redox reactions (involving both electron- and atom-transfer mechanisms) of transition-metal poryphrin complexes. Interest will be centered on redox reactions involving more than one electron. Investigations of reductions of dioxygen by dinuclear porphrin complexes involving two dissimilar metals will be continued. Four-electron oxidations of organic complexes by chlorite ion, catalyzed by porphrin complexes will be studied, as well as related electrochemical reactions. Hetrometallic dinuclear porphrin (and related) complexes of second and third row transition elements will be prepared and characterized by several methods in order to ellucidate novel types of metal-metal multiple bond.Oxidation-reduction reactions involving the transfer of several electrons from reductant to oxidant are not rare in nature or in technological applications, but such reactions have been studied relatively infrequently. Building on achievements of the prior period of NSF support, the PI has identified several diverse types of multi-equivalent redox reactions, all of which involve transition metal porphrin complexes as catalysts or reactants. There is a strong probability that increased understanding of such multi-electron redox reactions will have important technological and scientific applications. Four-electron oxidations by chlorite ion, to be studied in this program, are regarded as especially promising.

斯坦福大学的James Collman得到了无机，生物无机和有机化学计划的支持，研究过渡金属卟啉络合物的氧化还原反应（涉及电子和原子转移机制）。兴趣将集中在涉及一个以上电子的氧化还原反应上。将继续研究双核卟啉配合物涉及两种不同金属的还原。将研究亚氯酸根离子在卟啉配合物催化下对有机配合物的四电子氧化以及相关的电化学反应。第二和第三行过渡元素的异金属双核卟啉（及相关）配合物将通过多种方法制备和表征以阐明新型的金属-金属多重键。涉及多个电子从还原剂转移到氧化剂的氧化还原反应在自然界或在技术应用中并不罕见，但这类反应的研究相对较少。基于NSF前期支持的成就，PI已经确定了几种不同类型的多当量氧化还原反应，所有这些反应都涉及过渡金属卟啉络合物作为催化剂或反应物。有一个很大的可能性，增加了解这种多电子氧化还原反应将有重要的技术和科学应用。在这个计划中要研究的四电子氧化物，被认为是特别有前途的。