蒽醌和9-甲氧基蒽系统1,8,9位上扩展的超价五中心六电子（5c-6e）C(2)Z(2)O相互作用的分子内原子分析
Atoms-in-molecules analysis of extended hypervalent five-center, six-electron (5c-6e) C(2)Z(2)O interactions at the 1,8,9-positions of anthraquinone and 9-methoxyanthracene systems.
作者信息
Nakanishi Waro, Nakamoto Takashi, Hayashi Satoko, Sasamori Takahiro, Tokitoh Norihiro
机构信息
Department of Materials Science and Chemistry, Faculty of Systems Engineering, Wakayama University, 930 Sakaedani, Wakayama 640-8510, Japan.
出版信息
Chemistry. 2007;13(1):255-68. doi: 10.1002/chem.200600471.
To clarify the nature of five-center, six-electron (5c-6e) C(2)Z(2)O interactions, atoms-in-molecules (AIM) analysis has been applied to an anthraquinone, 1,8-(MeZ)(2)ATQ (1 (Z=Se), 2 (Z=S), and 3 (Z=O)), and a 9-methoxyanthracene system, 9-MeO-1,8-(MeZ)(2)ATC (4 (Z=Se), 5 (Z=S), and 6 (Z=O)), as well as 1-(MeZ)ATQ (7 (Z=Se), 8 (Z=S), and 9 (Z=O)) and 9-MeO-1-(MeZ)ATC (10 (Z=Se), 11 (Z=S), and 12 (Z=O)). The total electronic energy density (H(b)(r(c))) at the bond critical points (BCPs), an appropriate index for weak interactions, has been examined for 5c-6e C(2)Z(2)O and 3c-4e CZO interactions of the n(p)(O)sigma*(Z--C) type in 1-12. Some hydrogen-bonded adducts were also re-examined for convenience of comparison. The total electronic energy densities varied in the following order: OO (3: H(b)(r(c))=0.0028 au)=OO (6: 0.0028 au)>OO (9: 0.0025 au)> or =NNHF (0.0024 au)> or =OO (12: 0.0023 au)>>H(2)OHOH (0.0015 au)>SO (8: 0.0013 au)=SO (2: 0.0013 au)> or =SO (11: 0.0012 au)=SO (5: 0.0012 au)>HFHF (0.0008 au)=SeO (10: 0.0008 au)=SeO (4: 0.0008 au)> or =SeO (1: 0.0007 au)> or =SeO (7: 0.0006 au)>>HCNHF (-0.0013 au). H(b)(r(c)) values for SO were predicted to be smaller than the hydrogen bond of H(2)OHOH and H(b)(r(c)) values for SeO are very close to or slightly smaller than that for HFHF in both the ATQ and 9-MeOATC systems. In the case of Z=Se and S, H(b)(r(c)) values for 5c-6e C(2)Z(2)O interactions are essentially equal to those for 3c-4e CZO if Z is the same. The results demonstrate that two n(p)(O)sigma*(Z--C) 3c-4e interactions effectively connect through the central n(p)(O) orbital to form the extended hypervalent 5c-6e system of the sigma*(C--Z)n(p)(O)sigma*(Z--C) type for Z=Se and S in both systems. Natural bond orbital (NBO) analysis revealed that n(s)(O) also contributes to some extent. The electron charge densities at the BCPs, NBO analysis, and the total energies calculated for 1-12, together with the structural changes in the PhSe derivatives, support the above discussion.
为阐明五中心、六电子（5c - 6e）C(2)Z(2)O相互作用的本质，已对蒽醌1,8-(MeZ)(2)ATQ（1（Z = Se）、2（Z = S）和3（Z = O））、9 - 甲氧基蒽体系9 - MeO - 1,8-(MeZ)(2)ATC（4（Z = Se）、5（Z = S）和6（Z = O））以及1-(MeZ)ATQ（7（Z = Se）、8（Z = S）和9（Z = O））和9 - MeO - 1-(MeZ)ATC（10（Z = Se）、11（Z = S）和12（Z = O））进行了分子中的原子（AIM）分析。已针对1 - 12中n(p)(O)σ*(Z - C)类型的5c - 6e C(2)Z(2)O和3c - 4e CZO相互作用，研究了键临界点（BCP）处的总电子能量密度（H(b)(r(c))），这是弱相互作用的一个合适指标。为便于比较，还重新研究了一些氢键加合物。总电子能量密度按以下顺序变化：OO（3：H(b)(r(c)) = 0.0028 au）= OO（6：0.0028 au）> OO（9：0.0025 au）≥NNHF（0.0024 au）≥OO（12：0.0023 au）>>H(2)OHOH（0.0015 au）>SO（8：0.0013 au）= SO（2：0.0013 au）≥SO（11：0.0012 au）= SO（5：0.0012 au）>HFHF（0.0008 au）= SeO（10：0.0008 au）= SeO（4：0.0008 au）≥SeO（1：0.0007 au）≥SeO（7：0.0006 au）>>HCNHF（-0.0013 au）。在ATQ和9 - MeOATC体系中，预测SO的H(b)(r(c))值小于H(2)OHOH的氢键，且SeO的H(b)(r(c))值非常接近HFHF的H(b)(r(c))值或略小于它。在Z = Se和S时，如果Z相同，5c - 6e C(2)Z(2)O相互作用的H(b)(r(c))值与3c - 4e CZO的基本相等。结果表明，在两个体系中，对于Z = Se和S，两个n(p)(O)σ*(Z - C) 3c - 4e相互作用通过中心n(p)(O)轨道有效地连接起来，形成了扩展的超价5c - 6e体系σ*(C - Z)n(p)(O)σ*(Z - C)类型。自然键轨道（NBO）分析表明n(s)(O)也有一定贡献。BCP处的电子电荷密度、NBO分析以及为1 - 12计算的总能量，连同PhSe衍生物的结构变化，支持了上述讨论。
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