Heteroatomic deprotonation of substituted methanes and methyl radicals: Theoretical insights into structure, stability, and thermochemistry

Morris M.; Chan B.; Radom L.

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Heteroatomic deprotonation of substituted methanes and methyl radicals: Theoretical insights into structure, stability, and thermochemistry

机译：取代的甲烷和甲基的杂原子去质子化：结构，稳定性和热化学的理论见解

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High-level W1w ab initio calculations have been used to investigate the structural and thermochemical changes that result from heteroatomic deprotonation of CH3YH molecules and ?CH _2YH radicals (YH = BH_2, CH_3, NH_2, OH, AlH_2, SiH_3, PH_2, and SH). The thermochemical quantities considered include gas-phase acidities, various bond dissociation enthalpies, and heats of formation. The high-level ab initio results are compared with available experimental data and generally show excellent agreement. In a small number of cases in which we find discrepancies that persist at even higher theoretical levels (e.g., W4), we suggest that the experimental data should be re-examined. We find that the C-Y bond lengths of ?CH_2YH contract upon deprotonation, whereas for CH_3YH, the predicted effect, in general, is a lengthening of the C-Y bond. These structural changes, for the most part, are reflected in the changes to the C-Y bond dissociation enthalpies. The CH3YH molecules are calculated to be 50-200 kJ mol~(-1) less acidic in the gas phase than the corresponding ?CH_2YH radicals, indicating relative stabilization of the ?CH_2Y- radical anions. The structural and thermochemical changes are rationalized using a combination of resonance and orbital interaction arguments.

机译：已使用高级W1w从头算算来研究CH3YH分子和？CH _2YH自由基（YH = BH_2，CH_3，NH_2，OH，AlH_2，SiH_3，PH_2和SH）的杂原子去质子化导致的结构和热化学变化。。考虑的热化学量包括气相酸度，各种键离解焓和形成热。高水平的从头算结果与可用的实验数据进行了比较，通常显示出极好的一致性。在少数情况下，我们发现差异甚至在更高的理论水平上仍然存在（例如，W4），因此我们建议应重新检查实验数据。我们发现，去质子化时，？CH_2YH的C-Y键长度收缩，而对于CH_3YH，预测效果通常是C-Y键的延长。这些结构变化大部分反映在C-Y键离解焓的变化中。计算得出，CH3YH分子在气相中的酸度比相应的？CH_2YH自由基低50-200 kJ mol〜（-1），表明？CH_2Y-自由基阴离子相对稳定。通过共振和轨道相互作用的论证可以使结构和热化学变化合理化。

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《The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory》 |2012年第50期|共7页
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Morris M.; Chan B.; Radom L.;
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1. Heteroatomic deprotonation of substituted methanes and methyl radicals: Theoretical insights into structure, stability, and thermochemistry [J] . Morris M., Chan B., Radom L. The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory . 2012,第50期

机译：取代的甲烷和甲基的杂原子去质子化：结构，稳定性和热化学的理论见解
2. Heteroatomic deprotonation of substituted methanes and methyl radicals: Theoretical insights into structure, stability, and thermochemistry [J] . Morris M., Chan B., Radom L. The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory . 2012,第50期

机译：取代的甲烷和甲基的杂原子去质子化：结构，稳定性和热化学的理论见解
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机译：羟基自由基与乙烷和一系列Cl-和F-取代的甲烷在300-400DEGK下反应的动力学。 OH作为对流层水槽防止臭氧消耗

Heteroatomic deprotonation of substituted methanes and methyl radicals: Theoretical insights into structure, stability, and thermochemistry

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