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

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: 1 April 2012
Available Online: 8 June 2012
Fund Project: 国家自然科学基金(21173129)资助项目 (21173129)

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.
- Clycloaddition,
- α-H cleavage,
- Carbonyl compound,
- Density functional theory
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