Theoretical Study of the Heterolytic σ Bond Cleavage on the Ge=O Bond of Germanone. An Insight into the Driving Force from both Electronic and Dynamical Aspects.

Theoretical Study of the Heterolytic σ Bond Cleavage on the Ge=O Bond of Germanone. An Insight into the Driving Force from both Electronic and Dynamical Aspects.
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锗酮 Ge=O 键异解 σ 键断裂的理论研究，从电子和动力学方面洞察驱动力。

DOI：
10.1021/acs.jpca.6b12478
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发表时间：
2017
期刊：
J. Phys. Chem. A
影响因子：
2.9
通讯作者：
Toshiaki Matsubara and Tomoyoshi Ito
Toshiaki Matsubara and Tomoyoshi Ito
中科院分区：
化学3区
文献类型：
--
作者：
上山達也;高山京也;中川和輝;前田悠斗;小椋大聖;神谷亮汰;笹野準貴;若林優次;福成雅史;山口裕資;斉藤輝雄;立松芳典;Toshiaki Matsubara and Tomoyoshi Ito

文献摘要

相似文献

用量子力学(QM)和分子动力学(MD)方法研究了H2O、NH_3、Me_2C、σ、H_2、CH_4、BH_3和SiH_4在日耳酮Ge-O键上的键断裂机理。QM计算表明，所有衬底的σ键都是在极大极化的GeO键上异质断裂的。在σ键断裂之前，在H2O、Me2C、O和NH3的情况下，衬底首先接近GeO Ge，而在H2、CH4、BH3和SiH4的情况下，衬底首先接近GeO的氧。对于H2O、NH3和Me2CO，在σ键断裂之前存在底物与Ge配位的团簇，底物的这种配位对异质裂解σ键的断裂起着重要作用。对于H2O的情况也进行了QM-MD模拟，结果表明，H2O配位的团簇的动能主要集中在配位的H2O氧上，使H2O氧与Ge的配位键发生强烈的振荡。这种振荡在OHσ键断裂前进一步放大，这种振荡的动能将传递到OH键断裂的正常模式。因此，H2O氧的配位和振动被认为是O--H-σ键异解断裂的重要电子和动力学驱动力。
The mechanism of the σ bond cleavage of H2O, NH3, Me2CO, H2, CH4, BH3, and SiH4on the GeO bond of germanone is examined by means of both quantum mechanical (QM) and molecular dynamics (MD) methods. The QM calculations show that the σ bonds of all the substrates are heterolytically broken on the very largely polarized GeO bond. Before the σ bond cleavage, the substrate at first approach the GeO germanium in the cases of H2O, Me2CO, and NH3, and in contrast, the GeO oxygen in the cases of H2, CH4, BH3, and SiH4. For the cases of H2O, NH3, and Me2CO, a cluster in which the substrate coordinates to the Ge exists before the σ bond cleavage, and this coordination of the substrate plays an important role on the heterolytic σ bond cleavage. The QM-MD simulations are also conducted for the case of H2O, and they show that the kinetic energy of the H2O-coordinated cluster especially concentrates on the coordinated H2O oxygen to strongly oscillate the coordinate bond between the H2O oxygen and the Ge. This oscillation further enlarges just before the OH σ bond cleavage, and the kinetic energy of this oscillation would be transmitted to the normal mode of the OH bond breaking. Thus, the coordination and the vibration of the H2O oxygen was thought to be an important driving force of the heterolytic cleavage of the OH σ bond in both electronic and dynamical aspects.