ABSTRACT
Laser-ablated group 6 metal atoms react with NF3 and PF3 to form the simple lowest energy N[triple bond]MF3 and P[triple bond]MX3 products, and this investigation has been extended to AsF3. Mo and W atoms react with AsF3 upon excitation by laser ablation or UV irradiation to form stable trigonal As[triple bond]MF3 terminal arsenides. These molecules are identified by comparison of the closely related infrared spectra of the analogous phosphide species and with frequencies calculated by density functional theory and multiconfigurational second order perturbation theory (CASSCF/CASPT2). Computed CASSCF/CASPT2 triple bond lengths for the As[triple bond]MoF3 and As[triple bond]WF3 molecules are 2.240 A and 2.250 A, respectively. The natural bond orders calculated by CASSCF/CASPT2 decrease from 2.67 to 2.60 for P[triple bond]MoF3 to As[triple bond]MoF3 and from 2.74 to 2.70 for P[triple bond]WF3 to As[triple bond]WF3 as the arsenic valence orbitals are less effective than those of phosphorus in bonding to each metal atom and the larger metal orbital size becomes more compatible with the arsenic valence orbitals. The Cr atom reaction gives the arsinidene AsF=CrF2 product instead of the higher energy As[triple bond]CrF3 molecule as the Cr (VI) state is not supported by the softer pnictides.
