Issue 44, 2016

Ligand-dependent formation of ion-pair CuI/CuIII trifluoromethyl complexes containing bisphosphines

Abstract

We report novel ion-pair bisphosphine CuI/CuIII trifluoromethyl complexes [(P2)2CuI]+[CuIII(CF3)4] (P2 = DPPE, BINAP or Xantphos) featuring tetrahedral CuI and square planar CuIII units that are prepared via oxidative trifluoromethylation of CuI with CF3SiMe3 in the presence of AgF. The bisphosphine CuI/CuIII CF3 complexes are highly reactive for aerobic trifluoromethylation of arylboronic acids to produce trifluoromethylated arenes in good to quantitative yields, which is in sharp contrast to the CuI/CuIII complex with phen/PPh3 ligands (1′). These results not only provide strong evidence that both the neutral and ion-pair CuIII CF3 complexes are competent catalytic species for Cu-mediated oxidative trifluoromethylation reactions, but also have important mechanistic implications that the active catalyst and reaction mechanism should be distinct and ligand-dependent for trifluoromethylation reactions with different types of ancillary ligands.

Graphical abstract: Ligand-dependent formation of ion-pair CuI/CuIII trifluoromethyl complexes containing bisphosphines

Supplementary files

Article information

Article type
Communication
Submitted
29 Jul 2016
Accepted
26 Aug 2016
First published
26 Aug 2016

Dalton Trans., 2016,45, 17588-17592

Ligand-dependent formation of ion-pair CuI/CuIII trifluoromethyl complexes containing bisphosphines

S. Zhang and W. Bie, Dalton Trans., 2016, 45, 17588 DOI: 10.1039/C6DT03016E

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements