3 years ago

Alkali Metal Chlorine and Bromine Carbenoids: Their Thermal Stability and Structural Properties

Alkali Metal Chlorine and Bromine Carbenoids: Their Thermal Stability and Structural Properties
Viktoria H. Gessner, Sebastian Molitor
The synthesis and structures of a series of M/X carbenoids of the type [Ph2P(S)]2CMX with M=Li, Na, and K and X=Cl and Br are reported, amongst the first isolated Na/Br and K/Br carbenoids. NMR spectroscopic as well as crystallographic studies showed distinct differences between the lithium carbenoids and their heavier congeners. In the solid state, all carbenoids showed no direct metal–carbon interaction, but an interaction between the metal and the halogen atom. This contact is only very weak in the case of the Li/Br carbenoid, but much more pronounced in the corresponding potassium and sodium compounds. Nevertheless, these interactions did not significantly influence the stability of the carbenoids by weakening the C−X bond and facilitating the MX elimination. As such all compounds were found to be stable up to approximately 60 °C in solution. Hence, M−X interactions—albeit being an essential feature for the structure formation of carbenoids—are not the only criterion determining the stability of such compounds. In the present systems, the stabilization by the thiophosphinoyl moieties is more important than the metal/halogen combination. Room-temperature stable carbenoids with different metal/halogen combinations were isolated and characterized, amongst the first sodium and potassium bromine systems. Metal–halogen interactions were found to be important factors for structure formation, but did not significantly influence the stability of the carbenoids.

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

DOI: 10.1002/chem.201701911

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.