含-CHO, -NO_2, -NH_2及-OH等官能基芳香類分子之分子內氫鍵鍵次之研究

The Intra-Molecular Hydrogen Bond Order Study of the -CHO, -NO_2, -NH_2 and -OH Substituted Aromatic Molecules

陳成(Cheng Chen) ； 葉世傑(Shyh-Jye Yeh) ； 孫光中(Kung-Chung Sun)

《化學》 53卷1期 (1995/03) Pp. 35-44

https://doi.org/10.6623/chem.1995004

摘要

以PM3分子軌域法幾何優選之結構、半經驗法分子軌域之P_uv及區域化鍵分佈分析法計算鄰位含-NO_2, -CHO、-OH、-NH_2及-CH_3雙官能基之苯環分子內氫鍵鍵次，證實含分子內氫鏈之分子按強弱順序各為o-C_6H_4(NO_2)OH、o-C_6H_4(CHO)OH、o- C_6H_4(NO_2)NH_2、o-C_6H_4(CHO) NH_2及o-C_6H_4(NO_2) CHO，其餘分子無顯著的分子內氫鍵之存在。本文首次發現所有含-CHO基分子，均有-CHO官能基O與本身之H間之強氫鍵，鍵次在0.29至0.25間，在一切分子內氫鍵次上限0.22之上，且與分子內(官能基間)氫鍵有強弱互補的現象。然而，官能基內有氫鍵存在與目前一般之觀念不符，我等將進行“區域化鍵能”之計算做進一步之認定。

關鍵字

分子內氫鍵 ； 官能基內氫鍵 ； 鍵次 ； PM3分子軌域 ； 半經驗法分子軌域

並列摘要

The intramolecular hydrogen bond orders for the ortho type double functional groups substituted benzene molecules can be calculated using semiempirical MO method. The functional groups include –NO_2, -CHO, -NH_2, and –CH_3. The order of the hydrogen bond strength within these molecules are found to be: o-C_6H_4(NO_2)OH＞o-C_6H_4(CHO)o-C_6H_4(NO_2)NH_2＞o-C_6H_4(CHO)NH_2＞o-C_6H_4(NO_2)CHO. In addition to the intra-molecular hydrogen bond, an intra-functional group hydrogen bond within the -CHO group with the quite strong bond order values of 0.25 to 0.29 is also found. Furthermore, there is a compensation effect between the intra-molecular and intra-functional group bond orders.

並列關鍵字

Intramolecular hydrogen bond ； Intrafunctional group hydrogen bond order ； PM3 MO ； semiempirical MO