第2楼2005/05/13
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Spin densities in dialkoxy-[16]annulene anion radicals: dimerization of alkoxy-[8]annulenes.
J Org Chem. 2003 Feb 21;68(4):1464-9.
The anion radicals of alkoxy-substituted cyclooctatetraenes in hexamethylphosphoramide spontaneously dimerize to form the dianions of dialkoxy-[16]annulenes. The dianions reveal the expected high-field NMR resonance for the internal protons. After electron transfer, the EPR spectra of the corresponding anion radicals reveal that only the 1,5-dialkoxy systems are formed. Further, the measured proton and (13)C spin densities show that the odd electron resides in a molecular orbital with six hydrogens in "deep" nodal positions that completely hide them from EPR detection. This MO corresponds to the nonbonding (singly occupied) MO of higher energy after splitting of the degenerate nonbonding MOs by the two-electron-withdrawing substituents. The surprising electron-withdrawing nature of the alkoxy substituents is attributed to a rather strong mixing of the sigma and pi systems in [16]annulene.
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Organometallic dehydro[14] annulenes containing Vollhardt's cyclobutadiene: are CpCo-complexed cyclobutadienes more aromatic then benzene?
Pd-catalyzed coupling of 1,2-diethynyl-3,4-(bistrimethylsilyl)cyclobutadienecyclopentadienylcobalt to a series of 1-iodo-2-(trimethylsilylethynyl)benzenes and 1-chloro-4-trimethylsilylbut-1-ene-3-yne is followed by desilylation with potassium carbonate. Cu(OAc)(2)-promoted oxidative ring closure leads to dehydro[14]annulenes and dehydro[14]benzoannulenes fused to a cyclobutadiene(cyclopentadienylcobalt) complex. Five of these fused dehydroannulenes were structurally characterized. (1)H NMR spectroscopy of the organometallic dehydro[14]annulenes incorporating the (bistrimethylsilyl)cyclobutadiene(cyclopentadienylcobalt) unit suggested that the aromaticity of the fused cyclobutadiene complex might be stronger than that of benzene according to the ring-current criterion.