Design of Polycyclic Molecules of Group 15 Elements and Pentagon Stability

15族元素多环分子设计及五边形稳定性

• 批准号: 14540470
• 负责人: INAGAKI Satoshi
• 金额: $ 1.92万
• 依托单位: Gifu University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2002
• 资助国家: 日本
• 起止时间: 2002 至 2003
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-14540470/
• 关键词: orbital phase; ring strain; strain energy; bond model analysis; pentagon stability; higher-row elements; polycyclic molecules; transition state; カルベン; シリレン; ゲルミレン; リン; ヒ素; 多環状化合物

We showed that the five-membered ring is the most stable of the monocylic molecules (XH)n (XN,P,As) composed of the 15 group elements and designed mono-and polycyclic molecules with low strains.A lone pair of an atom in the 15 group delocalize in a cyclic manner since the phase of the n-orbital for the lone pairs and the σ^*-orbitals of the vicinal X-X bonds is continuous. The bond model analysis showed that n-σ^* interaction does not contribute to significant stabiizization for X=N but for X=P and As. The five membered ring is more strained than the six-membered ring for X=N. To our surprise, the five-membered rings (X=P and As) have negative strain energies, and are less strained than the six-membered rings. According to the pentagon stability, we designed polycycic molecules of P and As with low strains.We showed the pentagon stability of the chemical species, aluminum anion, carbene, silylene, and germylene, where an carbon atom of cyclopentane is replaced by the corresponding atom.The pentagon stability is shown for the transition states of chemical reactions. For example, the activation energy (4.25) kcal/mol) of the deprotonation from cyclopentane is lower than that (4.52 kcal/mol) from cyclohexane.

我们表明，五元环是由15个组元素组成的单核分子（XH）N（XH）N（XH）N（Xn，P，AS），设计的单与多环状分子与低应变的单一和多环状分子。在15个组中以n-orbital和n-orbital的相位，以及15个组中的原子，以及n-orbital的相位，以及n-orbital的相位，以及n-orbital的相位。 X-X键是连续的。键模分析表明，n-σ^*相互作用不会导致x = n的显着稳定性，而是x = p和as。五个成员环比x = n的六元环更紧张。令我们惊讶的是，五元的环（x = p和as）具有负应变能，而不是六元环的紧张。根据五角大楼的稳定性，我们设计了P的多环芳烃分子和低菌株。我们显示了化学物种，铝阴离子，卡宾，甲基烯，西林和生殖的五角大楼稳定性，在那里环烷烷的碳原子被相应的原子质替代。例如，从环戊烷中去质子化的质子化活化能（4.25）kcal/mol比环己烷的（4.52 kcal/mol）低。

项目成果

Jing Ma: "Pentagon Stability : Cyclic Delocalization of Lone Pairs through σ Conjugation and Design of Polycyclophosphanes"Inorganic Chemistry. 41. 1876-1882 (2002)

马晶：“五边形稳定性：通过σ共轭和聚环磷烷的设计实现孤电子对的循环离域”无机化学41。1876-1882（2002）

Jing Ma, Atsushi Hozaki, Satoshi Inagaki: "Pentagon Stability in Cycloarsanes"Phosphorus, Sulfur, and Silicon. 177. 1705-1708 (2002)

Jing Ma、Atsushi Hozaki、Satoshi Inagaki：“环砷烷的五角大楼稳定性”磷、硫和硅。

Jing Ma: "Pentagon Stability : Cyclic Delocalization of Lone Pairs through σ Conjugation and Design of Polycyclophosphanes"Inorganic Chemistry. 41 7. 1876-1882 (2002)

马晶：“五边形稳定性：通过σ共轭和多环磷烷设计实现孤电子对的循环离域”无机化学41 7. 1876-1882 (2002)

Jing Ma: "Pentagon Stability in Cycloarsanes"Phosphorus, Sulfur, and Silicon. 177. 1705-1708 (2002)

马晶：“环砷烷中的五边形稳定性”磷、硫和硅。

Jing Ma, Atsushi Hozaki, Satoshi Inagaki: "Pentagon Stability : Cyclic Delocalization of Lone Pairs through σ Conjugation and Design of Polycyclophosphanes"Inorganic Chemistry. 41,7. 1876-1882 (2002)

Jing Ma、Atsushi Hozaki、Satoshi Inagaki：“五角大楼稳定性：通过 σ 共轭和多环磷烷的设计实现孤电子对的循环离域”无机化学 41,7（2002）。