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Aromaticity of tri- and tetranuclear metal-carbonyl clusters based on magnetic criteria
Clémence Corminboeuf1, Paul von Ragué Schleyer, R Bruce King
1Department of Chemistry and Center for Computational Chemistry, University of Georgia, Georgia, Athens, Georgia 30602, USA. corminb6@ccqc.uga.edu
Abstract:
Recently, the sigma-aromaticity model proposed for cyclopropane by Dewar was employed to account for the stability of Group 8 trinuclear metal-carbonyl compounds [M(3)(CO)(12)] (M=Fe, Ru, Os). This paper further examines this hypothesis and provides the first quantitative evidence for the sigma-aromatic/antiaromatic nature of the [M(3)(CO)(12)]/[M(4)(CO)(16)] species based on structural and nucleus-independent chemical-shift analysis. In addition, the extent of electron delocalization in tetrahedral [M(4)(CO)(14)] and butterfly [M(4)(CO)(15)] is analyzed and compared to prototype cycloalkanes. While remarkable analogies exist between metal-carbonyls and cycloalkanes, transition metals provide additional overlap possibilities that affect both the ring strain and the magnetic properties of metal-carbonyl rings and cages.
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