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本文首次提出了化学反应过程中几何可能性的定量研究。在下列条件下:(1)反应过程中,惰性配位体的键长,立体角系数等参数保持不变;(2)惰性配位体的压缩性很小;(3)在不压缩其它配位体的条件下,某一配位体在配位球面漂移所需的活化能低于这一配位体所形成的化学键断裂时所需的相应能量。我们提出动态堆积模型。以此来模拟反应过程中各个配位体间的相对位置和运动、配位体之间间隙的大小与受压缩的程度,并计算在反应中间过程中能够容纳新的配位体的最大空缺。考虑到使惰性配位体压缩将产生很大的空间势垒,以UCp_3X为例说明了Lewis碱的配合与解离,金属-碳σ键的热分解以及一氧化碳插入反应的可能性。
This paper presents for the first time a quantitative study of the geometric possibilities in chemical reactions. Under the following conditions: (1) During the reaction, the bonding length, solid angle coefficient and other parameters of the inert ligand remain unchanged; (2) the inertness of the inert ligand is very small; (3) In the case of ligands, the activation energy required for a ligand to drift at the coordination sphere is lower than the corresponding energy required for breaking of the bond formed by the ligand. We propose a dynamic stacking model. In this way, the relative position and movement of each ligand in the reaction process, the size of the gap between the ligands and the degree of compression are simulated, and the maximum vacancy that can accommodate the new ligand in the middle of the reaction is calculated. Taking into account the inert ligand compression will produce a large space barrier UCp_3X as an example to illustrate the coordination and dissociation of Lewis base, metal-carbon σ bond thermal decomposition and the possibility of carbon monoxide insertion reaction.