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Abstract
A new approach to 5,5-fused heterocyclic derivatives of cyclopentadienylmanganese tricarbonyl and pentamethylruthenocene is presented. 1,2-Dicarbophenoxycyclopentadienyl complexes of manganese and ruthenium were hydrolyzed to 1,2-dicarboxylic acids. Oxalyl chloride converted the acids to chlorocarbonyls, which reacted with bis(trimethylsilyl)sulfide to give the cyclopentadienyl-fused thioanhydrides. Alternatively, dehydration of the diacids with trifluoroacetic anhydride closed the diacids to cyclopentadienyl-fused anhydrides. Treatment of the anhydrides with p-toluidine followed by oxalyl chloride led to cyclopentadienyl-fused carboxylic imides. This approach enables direct comparison of electron-deficient Mn(CO)3 and electron-rich Ru(Cp*) coordination environments on the 5,5-fused heterocycles. Spectroscopic data reveal systematic downfield NMR shifts and higher infrared carbonyl stretching frequencies for the manganese complexes, consistent with lower electron density in the Mn(CO)3 compared to Ru(Cp*). Crystallographic analyses confirm that heterocycle fusion occurs without significant perturbation of the metal–cyclopentadienyl geometry. Comparative analysis across the series demonstrates that metal-dependent effects are primarily electronic rather than structural, with the Mn(CO)3 and Ru(Cp*) fragments modulating electron distribution within the fused ligand framework.
Document Type
Article
Publication Date
7-1-2026
Digital Object Identifier (DOI)
10.3390/cryst16070409
Archival?
Archival
Repository Citation
Pokharel, Uttam R.; Parkin, Sean; and Selegue, John P., "[5,5]-Fused Anhydride, Thioanhydride, and Imide Derivatives of Cyclopentadienyl Complexes" (2026). Chemistry Faculty Publications. 228.
https://uknowledge.uky.edu/chemistry_facpub/228
Notes/Citation Information
Publisher Copyright: © 2026 by the authors.