Kinetic evidence for the template effect of added cations on the rate of formation of benzo-18-crown-6 in water solution
Kinetic evidence for the template effect of added cations on the rate of formation of benzo-18-crown-6 in water solution
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添加阳离子对水溶液中苯并-18-冠-6 形成速率的模板效应的动力学证据
DOI：
10.1021/ja00465a052
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发表时间：
1977
影响因子：
15
通讯作者：
B. Masci
中科院分区：
文献类型：
--
作者：
L. Mandolini;B. Masci
让我们比较一下配体是o2的情况，这里的f值应该接近90因为键是离子型的。它应该更接近90，因此会非常小。因此，如果电离是在O is或F is中进行的，则不太可能出现任何卫星。另一方面，如果电离发生在cu2p轨道上，价电子会被吸引到cu3d轨道上，空穴会被吸引到s3p轨道上。因此«< 90，卫星出现。铜与配体之间的共价键越小，卫星越小。这与实验结果一致。特别是，含硫配体的配合物具有非常弱的Cu 2p卫星，这可能是由于在许多Cu- s配合物中已知的Cu- s键的大共价。9
Let us compare to the case when the ligands are O2-or F. should here be closeto 90 since the bonding is fairly ionic. tshould be even closer to 90 and therefore—will be very small. Thus, if the ionization is donein O Is or F Is, it is not likely that any satellite will appear. If the ionization is done in Cu 2p on the other hand, the valence electrons will be attracted to the Cu 3d orbital and the hole to S 3p. Thus «< 90, and a satellite appears. 6 It is likely that the satellite will be smaller the smaller and that is the more covalent the bond between Cu and the ligand. This is in agreement with experi-ments. 4’7· 8 In particular, complexes with sulfur ligands have very weak Cu 2p satellites8 which thus may be explained by the large covalency of the Cu-S bond, known in a number of Cu-S complexes. 9