Transition Metal-Nitrogen Multiple Bonds

过渡金属-氮多重键

• 批准号: 9802822
• 负责人: Dennis Lichtenberger
• 金额: $ 29.8万
• 依托单位: University of Arizona
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 1998
• 资助国家: 美国
• 起止时间: 1998-08-15 至 2001-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=9802822&HistoricalAwards=false
• 关键词: Transition; Metal; Nitrogen; Multiple; Bonds

Dr. David Wigley, Chemistry Department, University of Arizona, is supported by the Inorganic, Bioinorganic, and Organometallic Chemistry Program for studies of the chemistry of transition metal-nitrogen multiple bonds. Organoimido ligands have long been used as ancillary groups to variable degrees of steric protection and to support metals in their highest oxidation states. However, highly reactive metal-imide moieties are not well known. The overall objective of this research is to gain a better understanding of transition metal-nitrogen multiple bonding and to develop new methods for utilizing metal-imido moieties. To extend the range of their reactions new metal-mediated alkene aziridination reactions will be developed using d2 metal-nitroso and -azo complexe with both stoichiometric and catalytic processes that involve imido intermediates being investigated. The probable metallacyclic intermediates in these aziridinations will be prepared by independent routes and examined as mechanistic probes. New imido complexes of ruthenium will be prepared and their utility as nitrene [NR] transfer reagents will be explored. Finally, metal-imido complexes will be developed as reagents for electrocyclic rearrangements of value to synthetic organic chemistry.Highly reactive metal-imide groups, which are composed of a transition metal bonded to a nitrogen that bears a single additional substituent, can be generated under certain conditions. These metal-imido complexes activate C-H bonds in methane; play a central role in the industrially important hydroamination of olefins and olefin aziridination; and have been used to model steps in hydrodenitrogenation, propylene ammoxidation, and nitrile reduction catalysis. Despite the importance of reactive metal-imido complexes, their numbers remain small and their properties are not well systematized. In this research a number of new imido complexes will be prepared, new methods for activating metal imido groups will be developed, and the range of their reactions will be extended.

亚利桑那大学化学系戴维·威格利（David Wigley）博士得到了无机，生物无机和有机金属化学计划，用于过渡金属氮多键的化学研究。长期以来，有机胺配体一直被用作辅助组，以延伸到变量的固定度，并在其最高的氧化状态下支持金属。但是，高反应性金属含量部分尚不清楚。这项研究的总体目的是更好地了解过渡金属氮多键键并开发使用金属imido部分的新方法。为了扩展其反应的范围，将使用D2金属硝基和-azo复合物开发新的金属介导的烯烃氮化反应，并具有化学计量和催化过程，涉及涉及Imido中间体的化学计量和催化过程。这些齐里胶中的可能的金属中间体将通过独立路线制备，并作为机械探针进行检查。将准备新的ruthenium的imido综合体，并将探索它们作为硝基[NR]转移试剂的效用。最后，将金属imido络合物作为对合成有机化学价值重排的试剂进行开发某些条件。这些金属imido复合物激活甲烷中的C-H键。在烯烃和烯烃氮杂化的工业重要性水域中发挥着核心作用；并已用于模拟氢化硝化，丙烯氧化和硝酸氮还原催化的步骤。尽管反应性金属imido络合物很重要，但它们的数量仍然很小，并且其性能没有很好地系统化。在这项研究中，将准备许多新的Imido复合物，将开发用于激活金属Imido组的新方法，并将扩展其反应范围。