Modelling and Rationalizing Organometallic Chemistry with Computation: Where Are We?

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• 关键词：Bond activation ; Computational chemistry ; DFT ; Dispersion correction ; Mechanism ; Modelling ; Organometallics ; Selectivity
• 刊名：Structure & Bonding
• 出版年：2016
• 出版时间：2016
• 年：2016
• 卷：167
• 期：1
• 页码：1-37
• 全文大小：1,683 KB
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• 作者单位：Lionel Perrin (4)
  Kevin J. T. Carr (5)
  David McKay (5) (6)
  Claire L. McMullin (5)
  Stuart A. Macgregor (5)
  Odile Eisenstein (7)
  
  4. CNRS UMR 5246, Institut de Chimie et Biochimie Moléculaires et Supramoléculaires, CPE Lyon, Université Claude Bernard Lyon 1, 43 Boulevard du 11 Novembre 1918, 69622, Villeurbanne cedex, France
  5. Institute of Chemical Sciences, Heriot-Watt University, Edinburgh, EH14 4AS, UK
  6. School of Chemistry, University of St. Andrews, North Haugh, St. Andrews, KY16 9ST, UK
  7. Institut Charles Gerhardt, CNRS UMR 5253, Université de Montpellier, Place E. Bataillon, 34095, Montpellier, France
  
• 丛书名：Computational Studies in Organometallic Chemistry
• ISBN：978-3-319-31638-3
• 刊物类别：Chemistry and Materials Science
• 刊物主题：Chemistry
  Inorganic Chemistry
  
• 出版者：Springer Berlin / Heidelberg
• ISSN：1616-8550
• 卷排序：167

文摘

In this chapter, a perspective on how the field of applied computational organometallic chemistry has developed since the mid-1980s is presented. We describe the way in which the modelling of chemical systems has evolved over time, using metallocene chemistry as an example, and highlight the successes and limitations of simple models that were mandatory in the early days of the discipline. A number of more recent case studies are then presented where the full experimental system is now employed and a more quantitative outcome is sought. This includes examples from the Ce-mediated hydrogenation of pyridine, Rh-catalysed C–H bond activation and functionalization, Pd-catalysed azidocarbonylation and phenyl iodide activation at Ru(II) complexes. We conclude with our take on the title question.