In an aqueous solution, 63Cu chemical shielding order ([CuCl4]3− \simeq[CuBr4]3−<[CuI4]3−) and line widths (10 to 30 kHz) for CuX–KX systems(where X=Cl, Br, I) have been obtained. The chemical shift(−694 ppm) between [CuCl4]3− and [Cu(CN)4]3− is interpreted by the paramagnetic term which depends mainly upon a 3d-hole on a Cu(I) atom by using perturbation theory with an average excitation energy approximation. The linebroadening of Cu(I) halide complexes in aqueous solution is explained dominantly by a Cu(I) nuclear quadrupole interaction with the electric field gradient which arises from a 3d-hole on a Cu atom. For the abnormal increasing metal shielding order of [MX4](4−i)−([MCl4](4−i)−≤[MBr4](4−i)−<[MI4](4−i)−), a possibility of the heavyatom effect in the metal shielding of [CuI4]3−(649 ppm, using the lowest excitation energy of the diatomic molecule) and [CdI4]3−(1941 ppm using the lowest excitation energy of the diatomic molecule), is evaluated.
在
水溶液中,获得了 CuX-KX 系统(其中 X=Cl、Br、I)的 63Cu
化学屏蔽顺序([CuCl4]3- (simeq[CuBr4]3-<[CuI4]3-)和线宽(10 至 30 kHz)。利用平均激发能量近似的扰动理论,[CuCl4]3- 和 [Cu(CN)4]3- 之间的化学位移(-694 ppm)可以用顺磁项来解释,该顺磁项主要取决于 Cu(I)原子上的 3d 空穴。在水溶液中,Cu(I) 卤化物配合物的线宽主要由 Cu(I) 核四极与电场梯度的相互作用来解释,而电场梯度是由 Cu 原子上的 3d 孔产生的。针对[MX4](4-i)-([MCl4](4-i)-≤[MBr4](4-i)-<[MI4](4-i)-)金属屏蔽顺序的异常递增,评估了重原子效应在[CuI4]3-(649 ppm,使用二原子分子的最低激发能)和[CdI4]3-(1941 ppm,使用二原子分子的最低激发能)
金属屏蔽中的可能性。