Donor Complexes of Silylene, Germylene, and Stannylene

Donor Complexes of Silylene, Germylene, and Stannylene
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亚甲硅基、亚甲锗烷和亚锡基的供体配合物

DOI：
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发表时间：
1997
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通讯作者：
R. Schneider
R. Schneider
中科院分区：
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文献类型：
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作者：
W. Schoeller;R. Schneider

文献摘要

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利用所有价电子基组和相对论校正有效核心势方法，通过从头开始水平的量子化学研究，研究了各种供体分子 AH(3)（A = N、P、As、Sb、Bi）和 AH(2)（A = O、S、Se、Te）与亚甲硅基、亚甲甲锗烷基和亚锡基（(1)A(1) 基态）的配合物。因此，供体分子的结合较弱，缔合能在每摩尔15-30 kcal的范围内。加合物形成的放热能，即供体配合物的结合能，按亚甲硅基 > 亚甲锗烷基 > 亚锡基的顺序降低。群体分析表明，NH3 和 BiH3 仅与 XH2 片段（X = Si、Ge、Sn）形成弱键合，而高级同系物（A = P、As、Sb）形成叶立德结构，本质上是 1.2-偶极。已经针对亚甲硅基研究了两个供体分子的加成，但其效果远不如供体单加成有利。对于供体单加成，检查了 (a) 供体的 HOMO 能量（AH(3) 单元的 n 轨道，AH(2) 的 n、p 轨道）和 (b) 共价键能（来自文献）与供体-受体化合物的结合能之间的双参数关系。这个双参数方程令人满意地描述了供体-受体结构稳定性的基本特征。
The complexes of various donor molecules, AH(3) (A = N, P, As, Sb, Bi) and AH(2) (A = O, S, Se, Te) with silylene, germylene, and stannylene ((1)A(1) ground state) were studied by means of quantum chemical investigations at ab initio level utilizing all valence electron basis sets and relativistic corrected effective core potential methods. Accordingly, the donor molecules are weakly bound, the association energies are in the range of 15-30 kcal per mole. The exothermic energies for adduct formation, i.e., the resulting binding energies for the donor complexes, decrease in the order silylene > germylene > stannylene. The population analysis indicates for NH3 and BiH3 only a weak bonding towards the XH2 fragment (X = Si, Ge, Sn) while the higher homologues (A = P, As, Sb) form ylide structures, 1.2-dipolaric in nature. The addition of two donor molecules has been studied for silylene and is much less favourable than donor mono-addition. For the donor mono-addition a dual parameter relationship between (a) the HOMO energies of the donor (n-orbital of the AH(3) unit, n, p-orbitals for AH(2)) and (b) the covalent bond energies (from the literature) versus the binding energies of the donor-acceptor compounds was examined. This dual parameter equation describes satisfactorily the essential features of the stabilities of the donor-acceptor structures.