We assess the performance of six density functionals, each paired with one of five basis sets (a total of 30 model chemistries) for the prediction of geometrical parameters in the coordination sphere of nine vanadium complexes (for a total of 270 structural analyses). We find that results are generally consistent over the range of functionals tested and that none fail drastically. For bond lengths, the model chemistry PBE0/QZVP performed the best overall (having a MAD of only 0.02 Å from experiment) yet PBE0/6-31G* provides nearly identical results. For bond angles, PBE0 also performed best overall and, when combined with the 6-31G* basis, produces one of the smallest error distributions of any model chemistry tested. We subsequently applied the PBE0/6-31G* model chemistry to understanding the mechanism of action of a [BIMPY]VCl3 catalyst in the polymerization of styrene (Sty) and vinyl acetate (VAc). Our results indicate that the [BIMPY]VCl3 catalyst operates through a unique, two-step reaction pathway: dehalogenation to form a reactive V(II) intermediate (a highly favorable process) followed by a potentially reversible OMRP to control the polymerization of vinyl acetate. Control over vinyl acetate is facilitated by both the higher reactivity of the radical species and the participation of the ester group in the trapping step. In both the Sty and VAc cases we predict relatively poor control of the polymerization with the vanadium catalyst, which is in good agreement with our experimental results.