The utility of a range of computational chemistry approaches for the prediction of the regioselectivity for hydroformylation processes and metal-ligand dissociation in a model organometallic system is considered to provide insight about computational strategies for use in catalysis. The hydroformylation reactions investigated are the Rh-catalyzed hydroformylation of terminal alkenes with triarylphosphine and chelating diphosphine ligands. As well, the dissociation of water from a Pt complex is considered to probe method effects on metal-ligand bonding. Several density functional theory (DFT) approaches and ab initio methods are considered. We demonstrate that the quality of the basis set selected for the calculations can play a vital role in the prediction of even the product distribution, and that correcting for basis set superposition error (BSSE) can be very important. As well, the study demonstrates a broad range of predictions achievable using a variety of DFT approaches, which is, as discussed, a manifestation of the challenges that are encountered for calculations involving transition metal molecular species, illustrating the critical need to gauge computational chemistry methods.