Issue 12, 2012

Forming trifluoromethylmetallates: competition between decarboxylation and C–F bond activation of group 11 trifluoroacetate complexes, [CF3CO2ML]

Abstract

A combination of gas-phase 3D quadrupole ion trap mass spectrometry experiments and density functional theory (DFT) calculations have been used to examine the mechanism of thermal decomposition of fluorinated coinage metal carboxylates. The precursor anions, [CF3CO2MO2CCF3] (M = Cu, Ag and Au), were introduced into the gas-phase via electrospray ionization. Multistage mass spectrometry (MSn) experiments were conducted utilizing collision-induced dissociation, yielding a series of trifluoromethylated organometallic species and fluorides via the loss of CO2, CF2 or “CF2CO2”. Carboxylate ligand loss was insignificant or absent in all cases. DFT calculations were carried out on a range of potentially competing fragmentation pathways for [CF3CO2MO2CCF3], [CF3CO2MCF3] and [CF3CO2MF]. These shed light on possible products and mechanisms for loss of “CF2CO2”, namely, concerted or step-wise loss of CO2 and CF2 and a CF2CO2 lactone pathway. The lactone pathway was found to be higher in energy in all cases. In addition, the possibility of forming [CF3MCF3] and [CF3MF], via decarboxylation is discussed. For the first time the novel fluoride complexes [FMF], M = Cu, Ag and Au have been experimentally observed. Finally, the decomposition reactions of [CF3CO2ML] (where L = CF3 and CF3CO2) and [CH3CO2ML] (where L = CH3 and CH3CO2) are compared.

Graphical abstract: Forming trifluoromethylmetallates: competition between decarboxylation and C–F bond activation of group 11 trifluoroacetate complexes, [CF3CO2ML]−

Supplementary files

Article information

Article type
Paper
Submitted
05 Nov 2011
Accepted
19 Dec 2011
First published
06 Feb 2012

Dalton Trans., 2012,41, 3395-3406

Forming trifluoromethylmetallates: competition between decarboxylation and C–F bond activation of group 11 trifluoroacetate complexes, [CF3CO2ML]

N. J. Rijs and R. A. J. O'Hair, Dalton Trans., 2012, 41, 3395 DOI: 10.1039/C2DT12117D

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