1,2-Thiaphosphetanes Synthesized

  • Author: ChemistryViews.org
  • Published: 23 January 2019
  • Copyright: Wiley-VCH Verlag GmbH & Co. KGaA
  • Source / Publisher: Chemical Communications/Royal Society of Chemistry
  • Associated Societies: Royal Society of Chemistry (RSC), UK
thumbnail image: 1,2-Thiaphosphetanes Synthesized

1,2-Oxaphosphetanes, i.e., four-membered rings containing neighboring P(V) and O atoms, are well known. 1,2-thiaphosphetanes containing P(V) and S, in contrast, are less well studied, and their P(III) derivatives have been unknown so far. Such four-membered rings could be useful ligands due to their ring strain and reactivity.


Arturo Espinosa Ferao, Universidad de Murcia, Spain, Rainer Streubel, University of Bonn, Germany, and colleagues have synthesized the first P(III) 1,2-thiaphosphetane complexes with group 6 metals (pictured, R = CPh3), as well as the free ligand. The team reacted Li/Cl phosphinidenoid complexes of the metals Cr, Mo, and W with propylene sulfide to obtain the desired 1,2-thiaphosphetane complexes as a mixture of two stereoisomers. The free 1,2-thiaphosphetane ligand (pictured in orange) was prepared from the molybdenum complex using ligand exchange with 1,2-bis(diphenylphosphino)ethane (dppe) in toluene.


The researchers confirmed the structure of the products using 31P NMR spectroscopy and X-ray diffraction measurements, as well as theoretical calculations. The electronic properties of the free ligand, particularly its small HOMO–LUMO gap, could make it useful for redox-cycling organocatalysts that switch between P(III) and P(V) species.


 

Article Views: 809

Sign in Area

Please sign in below

Additional Sign In options

Please note that to comment on an article you must be registered and logged in.
Registration is for free, you may already be registered to receive, e.g., the newsletter. When you register on this website, please ensure you view our terms and conditions. All comments are subject to moderation.

Article Comments - To add a comment please sign in

Bookmark and Share

If you would like to reuse any content, in print or online, from ChemistryViews.org, please contact us first for permission. more


CONNECT:

ChemistryViews.org on Facebook

ChemistryViews.org on Twitter ChemistryViews.org on YouTube ChemistryViews.org on LinkedIn Sign up for our free newsletter


A product of ChemPubSoc Europe (16 European Chemical Societies)and Wiley-VCH