羰基化合物在Si(100)表面[2+2]环加成和<em>α</em>-H裂解反应的选择性

引用本文: 张继超, 程学礼, 程玉桥, 孟祥华, 刘永军, 刘成卜. 羰基化合物在Si(100)表面[2+2]环加成和α-H裂解反应的选择性[J]. 物理化学学报, 2012, 28(08): 1849-1853. doi: 10.3866/PKU.WHXB201206081 shu

Citation: ZHANG Ji-Chao, CHENG Xue-Li, CHENG Yu-Qiao, MENG Xiang-Hua, LIU Yong-Jun, LIU Cheng-Bu. Selectivity of [2+2] C＝O Cycloaddition and α-H Cleavage of Carbonyl Compounds on Si(100) Surface[J]. Acta Physico-Chimica Sinica, 2012, 28(08): 1849-1853. doi: 10.3866/PKU.WHXB201206081 shu

羰基化合物在Si(100)表面[2+2]环加成和α-H裂解反应的选择性

基金项目:
国家自然科学基金(21173129)资助项目 (21173129)

摘要:

最近研究表明: 丙酮能与半导体Si(100)表面发生[2+2]环加成和α-H 裂解反应形成相应的Si―C键或Si―O键, 在半导体材料的合成方面具有重要意义. 为进一步弄清不同羰基化合物在Si(100)表面的反应机理,本文应用密度泛函理论方法在B3LYP/6-311++G(d,p)//6-31G(d)水平上较为系统地研究了一系列羰基化合物CH₃COR (R=CH₃, H, C₂H₅, C₆H₅)与Si(100)表面的反应. 研究结果表明: 不论是[2+2]环加成反应还是α-H 裂解反应都对应较低的反应势垒(小于25 kJ·mol^-1); 环加成反应的势垒比α-H 裂解反应的势垒略高; 羰基上的取代基对反应势垒的影响较少; α-H裂解反应产物为动力学和热力学控制产物; 对丁酮来说, 1-位和3-位H原子的裂解反应都比较容易, 势垒相差很小. 这些结果表明羰基化合物与Si(100)表面的反应将得到多种产物.

关键词:

English

Selectivity of [2+2] C＝O Cycloaddition and α-H Cleavage of Carbonyl Compounds on Si(100) Surface

1.
1. Geological Scientific Research Institute, Shengli Oilfield Company of SINOPEC, Dongying 257015, Shandong Province, P. R. China;
2. School of Chemistry and Chemical Engineering, Shandong University, Jinan 250100, P. R. China
Received Date: 01 April 2012
Available Online: 10 July 2012
Fund Project:
国家自然科学基金(21173129)资助项目

Abstract:

Recent studies have demonstrated that a simple ketone [acetone, (CH₃)₂C＝O)] reacts with the Si(100) surface in a [2+2] C＝O cycloaddition or by α-H cleavage to form Si―C and/or Si―O σ-bonds. To understand the reactivity of carbonyl compounds bearing different substitutes, the [2 + 2] C＝O cycloaddition and α-H cleavage of carbonyl compounds CH₃COR (R=CH₃, H, C₂H₅, C₆H₅) on Si(100) surface have been investigated using density functional theory at the B3LYP/6-311 ++ G(d,p)//6-31G(d) level. Our calculation results reveal that: (1) both cycloaddition and α-H cleavage corresponds to very low energy barriers (lower than 25 kJ·mol^-1), and the energy barrier for cycloaddition is slightly higher than α-H cleavage; (2) the substituents on the carbonyl compound [CH₃COR] has only a minor influence on the energy barrier; (3) the α-H cleavage reactions are thermodynamically and kinetically more favorable than cycloadditions; (4) for the α-H cleavage of butanone, reactions at C1 and C3 positions are competitive. These findings suggest that the reactions of ketone derivatives with Si(100) surface will generate multiple products.

Key words:

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1.
沈阳化工大学材料科学与工程学院沈阳 110142

羰基化合物在Si(100)表面[2+2]环加成和α-H裂解反应的选择性

English

Selectivity of [2+2] C＝O Cycloaddition and α-H Cleavage of Carbonyl Compounds on Si(100) Surface

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

羰基化合物在Si(100)表面[2+2]环加成和α-H裂解反应的选择性

English

Selectivity of [2+2] C＝O Cycloaddition and α-H Cleavage of Carbonyl Compounds on Si(100) Surface

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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