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Aromaticity of Tri‐ and Tetranuclear Metal–Carbonyl Clusters Based on Magnetic Criteria
Author(s) -
Corminboeuf Clémence,
Schleyer Paul von Ragué,
King R. Bruce
Publication year - 2007
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200601037
Subject(s) - aromaticity , antiaromaticity , cyclopropane , electron delocalization , chemistry , metal carbonyl , ring (chemistry) , delocalized electron , transition metal , ring strain , metal , computational chemistry , crystallography , molecule , organic chemistry , catalysis
Recently, the σ‐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 σ‐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.