Three W-VI crystal structures with multifarious metal-ligand bond types are used to theoretically predict homolytic metal-element bond enthalpies with 11 popular DFT functionals, MP2 wave function methods, and four common valence basis set/pseudopotentials in order to evaluate the accuracy and precision of the resultant bond enthalpy data. To our knowledge, for the first time, estimates of component metal-ligand sigma- and pi-bond strengths are computed. The WE (E = C, N, O) bond enthalpies have the consistent trend sigma > second pi > first pi. In contrast, the element-element BDE trend for the 2p homologues is second pi. > first pi > sigma for nitrogen and oxygen, and sigma > first pi > second pi for carbon. These differences may underpin the differences in stability trends and thus reactivity behavior for metal-element multiple bonds as compared to the element-element multiple bonds, and metal-element triple bonds versus their corresponding double bonded counterparts. For example, Odom et al. show that Mel nucleophilically attacks at the imide (M=N) rather than the nitride (M equivalent to N) ligand; the relative pi-bond strengths derived herein provide a thermodynamic rationalization for this site preference. In this study, it is deduced from the calculated thermodynamics that the W-oxo ligand is more congruous with a triple bond than a double bond, consistent with the bonding model set forth in the seminal 1961 Ballhausen-Gray paper.