Abstract
Cationic complexes [(diene)Co(η-C6Me6)]+ (diene is buta-1,3-diene (2a), 5-isopropyl-2-methylcyclohexa-1,3-diene (2b), cycloocta-1,3-diene (2c), and cyclohexa-1,5-diene (2d)) were synthesized by the reaction of [Co(η-C6Me6)2]+ (1) with dienes in a CH2Cl2-Me2CO mixture. In the absence of dienes, cation 1 undergoes hydrogenation to form [(1,2,3,4,5,6-HMCD-1,3)-Co(η-C6Me6)]+ (HMCD is hexamethylcyclohexadiene, 2e). Structures [2c–e]PF6 were determined by X-ray diffraction analysis. According to the DFT calculations, the Co-C6H6 bond in the complexes with conjugated dienes is stronger than that in the complexes with nonconjugated dienes.
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