A structural analysis is reported of roughly 150 transition-metal (TM)-chalcogenido complexes in a variety of chemical environments. With few exceptions, agreement between calculated and experimental geometries is excellent. The research provides convincing evidence that computational methods employed are adequately describing the bonding in these diverse T M complexes. Interesting trends in relative TMCh (RMc~J-RMc~) bond lengths are found. Experimental and computational data show that other than the zirconocene-and hafnocene-oxos there is similar behavior in relative bond lengths for widely varying TM-chalcogenido complexes. Relative bond lengths versus oxo (S-0, Se-0, and Te-0) in group IVB metallocenes tend to be larger than for other families of complexes and show less variation among the heavier chalcogens (Se-S, Te-S, and T e S e ) . Analysis of localized wave functions for CpZZrCh point to a greater contribution from a singly-bonded Zr-Ch structure (relative to Z1-Ch) when Ch is 0 compared to heavier chalcogens.Taken together, the data suggest that there is a fundamental difference in the Zr-oxo (and Hf-oxo) bond in relation to heavier chalcogens, consistent with recent experimental data. In previous studies of multiply bonded T M complexes we have focused on the ability of ECPs to make computations feasible for complexes incorporating even the heaviest transition metals. The present work also evaluates ECP methods for heavier main group (MG) elements. Thechalcogens (Ch) 0, S, Se, and Te are included in this study.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.
hi@scite.ai
10624 S. Eastern Ave., Ste. A-614
Henderson, NV 89052, USA
Copyright © 2024 scite LLC. All rights reserved.
Made with 💙 for researchers
Part of the Research Solutions Family.