Matrix Infrared Spectroscopic and Quantum Chemical Investigations of the Group 5 Transition Metal Atom and CX4 Molecule (X = H, F, and Cl) Reaction Products

Laser-ablated vanadium, niobium, and tantalum atoms were reacted with CH2X2, CHX3, and CX4 (X = F and Cl) molecules in condensing argon, and the products were investigated by matrix isolation infrared spectroscopy. The major reaction products are new CH2–MX2, CHX–MX2, HC–MX3, and XC–MX3 complexes. These reactive species were identified by comparing their matrix infrared spectra with frequencies, intensities, and isotopic shifts from density functional theory calculations. Product structures and energies from these calculations are also presented. Results from previously studied Group 4 and 6 metal reaction products are compared. Little change is found in the calculated metal–carbon bond lengths in the early first row CH2MF2 methylidene σ2π2 series; however, the methylidyne complexes HC­{}­MF3 show considerable increase in bond strength for the nominally σ2π1π1(Ti), σ2π2π1(V), and σ2π2π2(Cr) carbon­{}metal bonds left to right. The Group 5 HC­{}­MF3 complexes have only a plane of symmetry whereas the Group 4 and 6 analogues have 3-fold symmetry.