Computational studies of cis– and trans–isomer preferences of low-spin d6 [M(DABF)2A2]+ and [M(CO)4A2]+ complexes (M = Co, Rh, Ir; A = anionic ligand): spectator ligand π-backbonding and DFT exchange

[Display omitted] •Some d6 transition metal [M(DABF)2A2]+ complexes should prefer trans geometries.•Preferences for trans geometries trend with increasing ligand atom atomic number.•This conflicts with geometric predictions from the trans influence concept.•Energy decompositions suggest DFT exchange...

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Bibliographic Details
Published in:	Computational and theoretical chemistry Vol. 1200; p. 113235
Main Authors:	Bacchi, Samantha M., Waters, Cara M., Agunoye Jones, Oreoluwa A., Becker, Greg, Bryan, Alexander P., Easter, Tyler D., Evans, Mykayla G., Farace, Jessica M., Johnson, Kristopher D., Kasse, Julian M, LaCasse, Zane R., Aguillon Perea, Nancy M., LaMontagne, Abraham J., Miller, Ryan M., Mundorf, Kenneth W., Pappas, Fotis G., Pappas, Konstantinos G., Pho, Victoria L., Potocki, Christopher T., Polz, Megan A., Quintana, Rafael, Rodriguez, Edwin A., Rogman, Tyler R., Schindlbeck, Stacy J., Slagle, Justin A., Tariq, Sumrah, Valadez, Eulalio, Viereckl, Rudolf J., Vincent, Thomas R., Weiner, Elisa S., Westfall, Jennivee A., Wood, Nicholas M., Ylo, Isabelle T., Pixler, Alexander, Hoerchler, Katarzyna B., DeLio, Ashley M., Gilbert, Thomas M.
Format:	Journal Article
Language:	English
Published:	Elsevier B.V 01-06-2021
Subjects:	Cis/trans isomers Coordination complex DFT exchange Diazabutadiene Energy decomposition Trans influence DFT exchange Diazabutadiene Energy decomposition Trans influence Cis/trans isomers Coordination complex
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Summary:	[Display omitted] •Some d6 transition metal [M(DABF)2A2]+ complexes should prefer trans geometries.•Preferences for trans geometries trend with increasing ligand atom atomic number.•This conflicts with geometric predictions from the trans influence concept.•Energy decompositions suggest DFT exchange underlies the anomalous preferences. Computational studies of low spin d6cis– and trans–[M(DABF)2A2]+ complexes (M = Co, Rh, Ir; A = anionic ligand) employing multiple model chemistries find that cis geometries are preferred for complexes where the binding atom in A is high and/or to the left in the Periodic Table, while trans geometries are preferred for complexes where the binding atom is heavy or to the right of the Periodic Table. This holds despite the fact that consideration of the trans influence for the π-acceptor spectator DABF ligand suggest that all such complexes should prefer cis geometries. Energy decomposition analysis ties the phenomenon mostly to the degree of DFT exchange; that this benefits trans geometries more than cis geometries is thought to arise from the greater electronic symmetry of the former. This is supported by predictions for haloborane complexes [M(DABF)2(BX2)2]+. In contrast, [M(CO)4A2]+ complexes, containing better π-accepting CO spectator ligands (presumably higher in the trans influence series), are predicted to prefer cis geometries except for the halogen complexes [M(CO)4X2]+ (X = F, Cl, I), where no distinct preferences exist.
ISSN:	2210-271X
DOI:	10.1016/j.comptc.2021.113235