Institute for Advanced Study, College of Science, Department of Chemistry, Nanchang University, Nanchang, China.
Chemphyschem. 2012 Feb;13(3):741-50. doi: 10.1002/cphc.201100730. Epub 2012 Feb 3.
The mechanism of the 1,3-dipolar cycloaddition reaction of azidotrimethylsilane (ATS) onto nanographene (NG) is thoroughly investigated at the B3LYP/6-31G(d,p) level. Calculations reveal that the reaction occurs through a two-step reaction mechanism. The first step is the chemical adsorption and the second one is the decomposition of the thereby formed nitride upon thermal activation, giving rise to an N-bridged product ultimately. The latter is the rate-determining step. Two possible pathways are compared to show that the [3+2] channel is favored over the [3+4] channel. The former is a symmetric synchronous process, whereas the latter follows an asymmetric concerted way, which can be rationalized by means of the frontier molecular orbital (FMO) theory. The reactivity of NG is discussed in detail, revealing that it is the electron density at the functionalization site which dominates the reactivity rather than the energetic effect. As a result, the edge area is calculated to be much more reactive than the centre.
叠氮三甲基硅烷（ATS）与纳米石墨烯（NG）的 1,3-偶极环加成反应的机理在 B3LYP/6-31G(d,p)水平上进行了深入研究。计算表明，该反应通过两步反应机制进行。第一步是化学吸附，第二步是热激活时形成的氮化物的分解，最终生成 N 桥接产物。后者是速率决定步骤。比较了两种可能的途径，表明[3+2]通道优先于[3+4]通道。前者是对称同步过程，而后者遵循非对称协同方式，这可以通过前沿分子轨道（FMO）理论来合理化。详细讨论了 NG 的反应性，表明是功能化位点的电子密度而不是能量效应主导反应性。因此，计算出边缘区域的反应性比中心区域高得多。
