Department of Inorganic and Analytical Chemistry, Budapest University of Technology and Economics, (BUTE), Szent Gellért tér 4, 1521, Budapest, Hungary.
Dalton Trans. 2011 Jul 21;40(27):7193-200. doi: 10.1039/c0dt01685c. Epub 2011 Jun 10.
Four different mechanisms and the effect of bulky groups were studied in the reaction of ({HC[CMeN(R)]2}Si, R = 2,6-diisopropylphenyl) with white phosphorus. The carefully tested B3LYP-D, ωB97X-D, and SOS-MP2 methods, by the CCSD(T) method, with cc-pVTZ basis set provided consonant results which support the reliability of our results and the applicability of these methods. The dispersion energy contribution to the total energy is estimated to about ∼70 kJ mol(-1) which proves the essential role of dispersion corrected methods. Based on the computed results we suggest a new mechanism which is fully supported by the experimental conditions. The investigation of the bulky groups clearly demonstrates an internal catalytic feature which has an essential role in the reaction mechanism. Usually bulky substituents prevent or reduce the reactivity, in this case however, substituents promote the reaction.
研究了 ({HC[CMeN(R)]2}Si，R = 2,6-二异丙基苯基) 与白磷反应中的四种不同机制和庞大基团的影响。通过 CCSD(T)方法，使用 cc-pVTZ 基组，仔细测试的 B3LYP-D、ωB97X-D 和 SOS-MP2 方法提供了一致的结果，支持了我们结果的可靠性和这些方法的适用性。色散能对总能量的贡献估计约为 ∼70 kJ mol(-1)，这证明了需要使用色散校正方法。基于计算结果，我们提出了一种新的机制，该机制完全得到了实验条件的支持。对庞大基团的研究清楚地表明了内部催化特征，该特征在反应机制中起着重要作用。通常情况下，庞大的取代基会阻止或降低反应性，但在这种情况下，取代基反而促进了反应。
