Tungsten–Ligand Bond Strengths for 2p Elements Including σ- and π-Bond Strength Components, A Density Functional Theory and ab Initio Study

Abstract

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 σand π-bond strengths are computed. The WE (E = C, N, O) bond enthalpies have the consistent trend σ > second π > first π. In contrast, the element−element BDE trend for the 2p homologues is second π > first π > σ for nitrogen and oxygen, and σ > first π > second π 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 MeI nucleophilically attacks at the imide (MN) rather than the nitride (M ≡ N) ligand; the relative π-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.

Thermochemistry of Tungsten—3p Elements for Density Functional Theory, Caveat Lector!

“…The present research extends a previous study by Moulder et al for tungsten with the 2p main group elements (E = C, N, and O) . Both works use the same suite of methodologies to permit a solid basis of comparison between W 2p and W 3p databases.…”

“…The coordination chemistry of 3p main group elements (WE = Si, P, and S) is highly relevant in inorganic and organometallic chemistry and so are studied here to see how they compare and contrast with the reported thermochemistry of the 2p congeners. ,,, To this end, the present research takes advantage of the isoelectronic nature of silicon, phosphorus, and sulfur to carbon, nitrogen, and oxygen, respectively, to construct models with similar coordination environments.…”

“…Conversion of a reported W–nitrogen computational model , to a W–phosphorus computational model; color-coded dashed lines denote the studied bond homolyses.…”

“…Conversion of a reported W–oxygen complex , to its W–sulfur congener; color-coded dashed lines denote the bond homolysis comparisons.…”

“…DFT functionals (blue), valence basis sets (brown) explored, and post-Hartree–Fock wave function methods (green) examined for this research. ,− Adapted from ref .…”