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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Comparative G2(MP2) Molecular Orbital Study of B_3H_7XH_3 Donor-Acceptor Complexes (X = N, P, and As)
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Comparative G2(MP2) Molecular Orbital Study of B_3H_7XH_3 Donor-Acceptor Complexes (X = N, P, and As)

机译：B_3H_7XH_3供体-受体配合物（X = N，P和As）的比较G2（MP2）分子轨道研究

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摘要

B_3H_7XH_3 and H_3BXH_3 (X = N, P, and As) have been studied as donor-acceptor complex type at the G2-(MP2) level of theory. Both single- and double-bridged structures of B_3H_7 Lewis acid are taken into account. Although the double-bridged structure is energetically favored in the isolated state, the coordination prefers the single-bridged one. The monoborane adducts adopt the staggered arrangement with C_(3v) symmetry. The energetic analysis by natural bond orbital theory shows that the decrease of hyperconjugative contribution upon complexation in the B_3H_7 moiety has, as consequence, a loss of symmetry for B_3H_7XH_3 (X=P and As) complexes. In the two series, the coordination is the result of two opposing interactions. The first one is stabilizing, developed between a' symmetry fragment molecular orbitals, and is mainly of 3MO-4e nature. The second one is destabilizing and developed between occupied molecular orbitals (2MO-4e) of donor and acceptor fragments having a" symmetry. Furthermore, in the case of BH_3 complexes, the complexation is made along the C_3 axis that joined the two fragments, whereas for B_3H_7, it is mainly centered on the nonequivalent boron atom, but the two other ones are also weakly involved in the coordination through a suitable p orbital even if the donor fragment is not on the three boron triangle center.
机译：B_3H_7XH_3和H_3BXH_3（X = N，P和As）已作为理论上的G2-（MP2）水平研究为供体-受体复合体类型。 B_3H_7 Lewis酸的单桥和双桥结构都被考虑在内。尽管在隔离状态下大力支持双桥结构，但协调更倾向于单桥结构。单硼烷加合物采用C_（3v）对称的交错排列。通过自然键轨道理论进行的能量分析表明，B_3H_7部分中络合时超共轭贡献的降低导致B_3H_7XH_3（X = P和As）配合物的对称性丧失。在两个系列中，协调是两个相对相互作用的结果。第一个是稳定的，在对称碎片分子轨道之间发展，并且主要具有3MO-4e性质。第二个是不稳定的，在供体和受体片段的占据分子轨道（2MO-4e）之间具有对称对称性。此外，在BH_3配合物的情况下，沿着连接两个片段的C_3轴进行配合，而对于B_3H_7，它主要以不等价的硼原子为中心，但是，即使供体片段不在三个硼三角中心，另外两个原子也通过合适的p轨道微弱地参与配位。

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