Abstract
Polyfluorinated, electron-withdrawing, and sterically demanding supporting ligands are of significant value in chemistry. Here we report the assembly and use of a bis(pyrazolyl)borate, [Ph2B(3-(SF5)Pz)2]− that combines all such features, and involves underutilized pentafluorosulfanyl substituents. The ethylene and carbonyl chemistry of copper(i) supported by [Ph2B(3-(SF5)Pz)2]−, a comparison to the trifluoromethylated counterparts involving [Ph2B(3-(CF3)Pz)2]−, as well as copper catalyzed cyclopropanation of styrene with ethyl diazoacetate and CF3CHN2 are presented. The results from cyclopropanation show that SF5 groups dramatically improved the yields and stereoselectivity compared to the CF3.
Highlights
Substituents are the key to modulating the chemical and physical properties of molecules, including those of metal complexes and catalysts
The penta uorosulfanyl (SF5) is a noticeably underutilized uorinated substituent compared to the CF3 group in chemistry.[2]
Synthesis of the SF5-pyrazole In 1964, Hoover and Coffman reported that a reaction of alkyne 2 with diazomethane in diethyl ether at 0 C led to the formation of a mixture of isomeric products 1 and 3 (3 : 2) (Scheme 1).[14]
Summary
Substituents are the key to modulating the chemical and physical properties of molecules, including those of metal complexes and catalysts. We describe the synthesis of [Ph2B(3-(SF5)Pz)2]À and the effects of this ligand support on copper(I) as re ected in the structures and bonding of ethylene and CO complexes (which represent two classes of organometallic complexes with signi cant fundamental and practical signi cance),[11] and catalytic alkene cyclopropanation, as well as a direct comparison to the related tri uoromethylated analogs (Fig. 1).
Sign-in/Register to view highlights & summary Sign-in/Register to access full text options 
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a callDisclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.
