Forming trifluoromethylmetallates: Competition between decarboxylation and C-F bond activation of group 11 trifluoroacetate complexes, [CF 3CO 2ML] -

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, [CF 3CO 2MO 2CCF 3] - (M = Cu, Ag and Au), were introduced into the gas-phase via electrospray ionization. Multistage mass spectrometry (MS n) experiments were conducted utilizing collision-induced dissociation, yielding a series of trifluoromethylated organometallic species and fluorides via the loss of CO 2, CF 2 or "CF 2CO 2". Carboxylate ligand loss was insignificant or absent in all cases. DFT calculations were carried out on a rang..