CHEMISTRY STUDENTS CATHERINE MOULDER AND KRISTINA KAFLE HAVE ARTICLE CHOSEN AS JOURNAL COVER | Department of Chemistry

Covid-19 —UNT is offering a mix of in-person, partially in-person, and online/remote course deliveries for Fall 2020. Stay up to date on UNT's response, including return to campus plans.

UNT Banner
September 27, 2019

CHEMISTRY STUDENTS CATHERINE MOULDER AND KRISTINA KAFLE HAVE ARTICLE CHOSEN AS JOURNAL COVER

Congratulations to Catherine Moulder and Kristina Kafle, Chemistry graduate and undergraduate students working with Dr. Thomas Cundari, for having their article "Tungsten-Ligand Bond Strengths for 2p Elements Including σ- and π-Bond Strength Components, A Density Functional Theory and ab Initio Study" chosen as the cover for the September 19 edition of the Journal of Physical Chemistry A. Congratulations to Kristina Kafle and Catherine Moulder for designing the cover art and Kristina for hand-drawing it.

Abstract: Three WVI 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 σ- and 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.

You can view the article here.