Investigation of the properties of tris(2-cyanoethyl)phosphine by electrospray and Fourier transform ion cyclotron resonance mass spectrometries

Abstract

The small, ambidentate phosphine P(CH₂CH₂CN)₃(tcp) has been investigated by laser ablation Fourier transform ion cyclotron resonance (LA-FTICR) and electrospray mass spectrometries (ESMS), particularly with regard to its interaction with some alkali- and transition-metal monocations. These two different ionization and mass spectrometric techniques have been shown to be complementary for this phosphine. Complexes of the type [M(tcp)]⁺(M = H or alkali-metal cation) were observed using both techniques. Corresponding species were observed for M = Cu, Ag, Co and Ni using LA-FTICR. In the negative-ion LA spectra the phosphine provides a source of cyanide ions, forming metal–cyanide cluster anions of the type [M_x(CN)_{x+ 1}]^–. These are predominant for Cu, and less so for Ag, Co and Ni. Loss of acrylonitrile from the metal complexes also provides one of the main decomposition pathways which can be observed in both positive- and negative-ion modes, giving complexes of the type [M(CH₂CHCN)_x]⁺(x= 1 or 2) and [M(CN){P(CH₂CH₂CN)}]^– respectively.