13Cu、65Cu和15N标记的二(2-羟基苯乙酮肟)-铜(Ⅱ)配合物的ESR波谱研究

本文解析了同位素标记的⁶³Cu-¹⁴N-HAP,⁶⁵Cu-¹⁴N-HAP,⁶³Cu-¹⁵N-HAP。⁶⁵Cu-¹⁵N-HAP,和Cu-¹⁵N-HAP,等五种配合物在四氢呋喃中,在77K温度下测得的分辨较好的ESR波谱。从图上不仅得到了⁶³Cu和⁶³Cu的超精细分裂,而且还得出分辨较好的¹⁴N和¹⁵N的超超精细分裂。比较合理地确定了g_x,g_y,g_z;A_x⁶⁵,A_y⁶⁵,A_z⁶⁵和A_x⁶³,A_y⁶³,A_z⁶³以及A_⊥¹⁵,A_⊥¹⁵和A_⊥¹⁴,A_⊥¹⁴等张量参数。利用测得的波谱参数计算了键参数,并讨论了配合物的电子结构及成键特性,得到了较满意的结果。

STUDY ON ESR SPECTRA OF 63Cu, 65Cu AND 15N LABELLED BIS(2-HYDROXYLPHENYL KETOXIME) COPPER(Ⅱ) COMPLEXES

A better resolution of ESR spectra of labelled ⁶³Cu-¹⁴N-HAP,⁶⁵Cu-¹⁴N-HAP, ⁶³Cu-¹⁵N-HAP, ⁶⁵Cu-¹⁵N-HAP and Cu-¹⁵N-HAP complexes in tetrahydrofuran (THF) solution, measured at 77K, was analyzed. From the spectra, we have got not only hyperfine splitting of the ⁶³Cu and ⁶⁵Cu; but also very nice superhyperfine splitting arising from ¹⁴N and ¹⁵N nuclei. The g_x,g_y,g_z;A_x⁶⁵,A_y⁶⁵,A_z⁶⁵; A_⊥¹⁵,A_⊥¹⁵,A_⊥¹⁴,A_⊥¹⁴ etc. tensor parameters were determined rather reasonably. The bonding parameters were calculated by using measured spectral parameters, and its electronic structure and the bonding character of these complexes are discussed, and better satisfactory results were obtained.