期刊
JOURNAL OF ORGANIC CHEMISTRY
卷 65, 期 5, 页码 1448-1455出版社
AMER CHEMICAL SOC
DOI: 10.1021/jo991590q
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Molecular and electronic structural properties of the hydrogen-bonded complexes of p-quinone dianions (PQ(2-)) were investigated by electrochemistry and spectroelectrochemistry of PQ in MeCN combined with ab initio MO calculations. Hydrogen bonding between PQ(2-) and MeOH was measured as the continuous positive shift of the apparent second half-wave reduction potentials with increasing concentrations of MeOH. Detailed analyses of the behavior reveal that PQ(2-) forms the 1:2 hydrogen-bonded complexes at low concentrations of MeOH and the 1:4 complexes at high concentrations, yielding the formation constants. Temperature dependence of the formation constants allows us to yield the formation energy as 76.6 and 118.9 kJ mol(-1) for the 1:2 and 1:4 complex axion of the 1,4-benzoquinone dianion (BQ(2-)) with MeOH, respectively. These results show that the. pi- dianions involving the quinone arbonyl groups exhibit very strong hydrogen-accepting ability. The longest wavelength band of the spectra of BQ(2-) and the chloranil dianion (CL2-) is assigned to the B-1(au) <-- (1)A(g) band mainly contributed from an intramolecular charge-transfer (CT) configuration, Hydrogen bonding allows the band of BQ(2-) and CL2- to be blue-shifted, depending on the strength of the hydrogen bonds. CNDO/S-CI calculations reveal that the blue shift is ascribed to stabilization of the ground state by the hydrogen bonding involving strong n-sigma-type CT interaction. The HF/631G(d) calculation results show that the structure of PQ(2-) is characterized by a lengthening of the C=O bonds and a benzenoid ring. The geometrical properties of the hydrogen-bonded complexes of PQ(2-) are a slight lengthening of the C=O bonds and a short distance of the hydrogen bonds. It is demonstrated that this situation is due to the strong n-sigma CT interaction in the hydrogen bonds. The results suggest that the differing functions and properties of biological quinones are conferred by the n-sigma CT interaction through hydrogen bonding of the dianions with their protein environment.
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