3 years ago

Molybdenum(0) Dihapto-Coordination of Benzene and Trifluorotoluene: The Stabilizing and Chemo-Directing Influence of a CF3 Group

Molybdenum(0) Dihapto-Coordination of Benzene and Trifluorotoluene: The Stabilizing and Chemo-Directing Influence of a CF3 Group
W. Dean Harman, Steven J. Dakermanji, Katy B. Wilson, Jeffery T. Myers, Justin H. Wilde, Jacob A. Smith, Philip J. Shivokevich
The preparation of the complexes TpMo(NO)(DMAP)(η2-PhCF3) (5) and TpMo(NO)(DMAP)(η2-benzene) (3) is described. The CF3 group is found to stabilize the metal–arene bond strength in 5 by roughly 3 kcal/mol compared to that in 3, allowing the large-scale synthesis and isolation of the trifluorotoluene analogue (5, 37 g, 70%). When a benzene solution of 5 is allowed to stand, clean conversion to the benzene analogue 3 occurs, and this complex may be precipitated from solution upon the addition of pentane and isolated. The trifluorotoluene complex is shown to be a synthetic precursor to functionalized cyclohexadienes: In solution, it selectively protonates at the ortho position, and the resulting η2-arenium species undergoes reactions with nucleophiles at the adjacent meta carbon. Thus, reactions of 5, triflic acid, and either N-methylpyrrole or 1-methoxy-2-methyl-1-(trimethylsilyloxy)-1-propene result in 5-substituted-1,3-cyclohexadienes after removal of the metal.

Publisher URL: http://dx.doi.org/10.1021/jacs.7b05009

DOI: 10.1021/jacs.7b05009

You might also like
Discover & Discuss Important Research

Keeping up-to-date with research can feel impossible, with papers being published faster than you'll ever be able to read them. That's where Researcher comes in: we're simplifying discovery and making important discussions happen. With over 19,000 sources, including peer-reviewed journals, preprints, blogs, universities, podcasts and Live events across 10 research areas, you'll never miss what's important to you. It's like social media, but better. Oh, and we should mention - it's free.

  • Download from Google Play
  • Download from App Store
  • Download from AppInChina

Researcher displays publicly available abstracts and doesn’t host any full article content. If the content is open access, we will direct clicks from the abstracts to the publisher website and display the PDF copy on our platform. Clicks to view the full text will be directed to the publisher website, where only users with subscriptions or access through their institution are able to view the full article.