European Journal of Inorganic Chemistry
European Journal of Inorganic Chemistry
4 years ago

Enhanced Relative Stability of Metallabenzenes versus Metallocenes upon Ring Perfluorination: Nickel, Palladium, and Platinum Systems

Enhanced Relative Stability of Metallabenzenes versus Metallocenes upon Ring Perfluorination: Nickel, Palladium, and Platinum Systems
Yaoming Xie, Guoliang Li, Henry F. Schaefer, R. Bruce King, Jing Li
Perfluorination of one η5-C5H5 ring in the MC10H10 system (M = Ni, Pd, Pt) to give an MC10H5F5 system greatly destabilizes structures containing a perfluorinated pentahapto η5-C5F5 ring. As a result, the metallapentafluorobenzene structures (η5-C5H5)(MC5F5) are the lowest-energy structures for all three metals, with energy differences of 1.4, 6.2, and 16.2 kcal/mol for nickel, palladium, and platinum, respectively. In addition, palladium and platinum isomeric metallatetrafluorocyclopentadiene structures, with a complexed fluorobenzene ring; that is, (C6H5F)(MC4F4) (M = Pd, Pt), are lower-energy structures than the lowest-energy metallocene structures. Furthermore, for palladium and platinum, the lowest-energy metallocene structures are slipped metallocenes with a trihapto, rather than a pentahapto, pentafluorocyclopentadienyl ring. These theoretical results suggest the pentafluorocyclopentadienyl anion as a reagent for synthesizing metallapentafluorobenzene derivatives by reactions with (η5-C5R5)M(CO)X, (η5-C5R5)2M2(µ-CO)2, or (η5-C5R5)2Ni (R = H, Me; M = Ni, Pt).Perfluorination of one η5-C5H5 ring in the MC10H10 system (M = Ni, Pd, Pt) to give an MC10H5F5 system greatly destabilizes structures containing a perfluorinated pentahapto η5-C5F5 ring. As a result, the metallapentafluorobenzene isomers are the lowest-energy structures for all three metals.

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/ejic.201700810

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.