Hydride Dissociation Energies of Six-Membered Heterocyclic Organic Hydrides Predicted by ONIOM-G4Method
Hydride Dissociation Energies of Six-Membered Heterocyclic Organic Hydrides Predicted by ONIOM-G4Method
复制标题
ONIOM-G4方法预测六元杂环有机氢化物的氢化物解离能
DOI：
10.1021/ci2001567
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发表时间：
2012-01-01
影响因子：
5.6
通讯作者：
Fu, Yao
中科院分区：
文献类型：
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作者：
Shi, Jing;Huang, Xiong-Yi;Fu, Yao
氢化物解离能对理解有机氢化物的供氢能力具有重要意义。虽然一些有机氢化物的氢化物解离能已经被实验测量过，但从物理学的第一原理对这些量的研究却很少得到关注。在此，我们开发了一种ONIOM-G4方法，并仔细地将这种新方法与48种不同大体积分子的氢化物解离能进行了基准测试。结果表明，结合HF/6-31+G(d,p)//IEFPCM/Bondi1.15溶剂化模型，ONIOM-G4方法可以预测氢化物的解离能，误差仅为1.7 kcal/mol。利用新开发的ONIOM-G4方法，我们系统地研究了六类具有重要生物学和药学意义的六元杂环有机氢化物的氢化物解离能，即含有1,4-二氢吡啶、1,4-二氢吡嗪、1,4-恶嗪、1,4-噻嗪、4h -吡喃和4h -硫吡喃环结构的有机氢化物。建立了一个包含100多个六元杂环有机氢化物的广泛的氢化物解离能标，可用于合成有机化学和涉及氢化物阴离子转移的各种化学或生物过程的机理研究。
Hydride dissociation energy is of great importance in understanding the hydride-donating abilities of organic hydrides. Although the hydride dissociation energies of some organic hydrides have been experimentally measured, much less attention has been focused on the investigation of these quantities from the first principles of physics. Herein, we developed an ONIOM-G4 method and carefully benchmarked this new method against 48 experimental hydride dissociation energies of diverse bulky molecules. It was found that with the combined methods of the HF/6-31+G(d,p)//IEFPCM/Bondi1.15 solvation model, the ONIOM-G4 method can predict the hydride dissociation energies with an error bar of only 1.7 kcal/mol. With the newly developed ONIOM-G4 method, we then systematically studied the hydride dissociation energies of six categories of biologically and pharmaceutically important six-membered heterocyclic organic hydrides, namely, the organic hydrides containing 1,4-dihydropyridine, 1,4-dihydropyrazine, 1,4-oxazine, 1,4-thiazine, 4H-pyran, and 4H-thiopyran ring structures. An extensive hydride dissociation energy scale containing over 100 six-memebered heterocyclic organic hydrides has been established, which may find applications in both synthetic organic chemistry and mechanistic studies of various chemical or biological processes involving transferring of the hydride anion.