An Effective Core Potential Study of Transition-Metal Chalcogenides. 1. Molecular Structure


This article discusses an effective core potential study of transition-metal chalcogenides O, S, Se, and Te.

Creation Date: May 1994
UNT College of Arts and Sciences
UNT Scholarly Works
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Creator (Author):
Benson, Michael T.

Memphis State University

Creator (Author):
Cundari, Thomas R., 1964-

University of North Texas; Memphis State University

Creator (Author):
Lim, Soon J.

Memphis State University

Creator (Author):
Nguyen, Hoang D.

Memphis State University

Creator (Author):
Pierce-Beaver, Karen

Memphis State University

Publisher Info:
Publisher Name: American Chemical Society
Place of Publication: [Washington, DC]
  • Creation: May 1994

This article discusses an effective core potential study of transition-metal chalcogenides O, S, Se, and Te.

Department: Chemistry

Reprinted with permission from the Journal of the American Chemical Society. Copyright 1994 American Chemical Society.


Abstract: 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 TM complexes. Interesting trends in relative TMCh (Rмсh-Rмсh) bond lengths are found. Experimental and computational data show that other than the zirconocene-and halfnocene-oxos there is similar behavior in relative bond lengths for widely varying TM-chalcogenido complexes. Relative bond lengths versus oxo (S-O, Se-O, and Te-O) 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 Te-Se). Analysis of localized wave functions for Cp₂ZrCh point to a greater contribution from a singly-bonded Zr-Ch structure (relative to Zr=Ch) when Ch is O 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 TM complexes the authors 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. The chalcogens (CH) O, S, Se, and Te are included in this study.

Physical Description:

12 p.

Keyword(s): transition metals | chalcogenides | molecular structures
Source: Journal of the American Chemical Society, 1994, Washington DC: American Chemical Society, pp. 3955-3966
UNT College of Arts and Sciences
UNT Scholarly Works
  • DOI: 10.1021/ja00088a035 |
  • ARK: ark:/67531/metadc107778
Resource Type: Article
Format: Text
Access: Public
Publication Title: Journal of the American Chemical Society
Volume: 116
Issue: 9
Page Start: 3955
Page End: 3966
Peer Reviewed: Yes