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本文合成了硝酸钴(Ⅱ),氯化钴(Ⅱ),硫氰酸钴(Ⅱ)与内、外消旋的双(正-丙基亚砜)乙烷(以A表示)六个固体配合物:[Co_2(α-A)_3Cl_4]·H_2O、[Co(β-A)_2(NO_3)_2)·H_2O、[Co(β-A)_2(NO_3)_2]、[Co_2(α-A)_2(SCN)_4]·2H_2O和[Co(β-A)_2(SCN)_2](α-A和β-A各是外、内消旋的C_3H_7S(O)(CH_2)S(O)C_3H_7)。由元素分析、红外光谱、磁化率、电导及离子交换等研究结果表明配体A以二个氧原子与Co(Ⅱ)配位形成七元环的配合物。并确定Co_2(α-A)_3Cl_4为[Co(α-A)_3][CoCl_4]的配合物。初步认为[Co(α-A)(NO_3)]NO_3·H_2O为畸变的四面体配合物。其余四个配合物均为高自旋、畸变八面体,它们的结构可能是:及[Co(β-A)_2(SCN)_2]。对[Co(β-A)_2(NO_3)_2、[Co(β-A)_2(H_2O)_2](ClO_4)_2·H_2O及[Co(β-A)_2(SCN)_2]的Dq值计算结果表明NO_3~-、H_2O和SCN~-与Co(Ⅱ)配位符合配合物的光化序。
In this paper, six solid complexes of cobalt (II) nitrate, cobalt (II) chloride, cobalt thiocyanate (Ⅱ) and the internal and racemic bis (n-propyl sulfoxide) ethane [Co_2 (α-A) _3Cl_4] · H_2O, [Co (β-A) _2 (NO_3) _2) · H_2O, [Co (β-A) _2 (NO_3) _2] (O) (CH 2) S (O) 2 and (CO 2) 2 (SCN) 4] · 2H 2 O and [Co (β-A) C_3H_7). The results of elemental analysis, IR, magnetic susceptibility, conductivity and ion exchange show that ligand A coordinates with Co (Ⅱ) to form seven-membered ring complexes with two oxygen atoms. And it was confirmed that Co_2 (α-A) _3Cl_4 is a complex of [Co (α-A) _3] [CoCl_4]. It is preliminarily believed that [Co (α-A) (NO_3)] NO_3 · H_2O is a distorted tetrahedral complex. The other four complexes are highly spin, distorted octahedron, their structure may be: and [Co (β-A) _2 (SCN) _2]. The Dq values of [Co (β-A) _2 (NO_3) _2, [Co (β-A) _2 (H_2O) _2] (ClO_4) _2 · H_2O and [Co (β-A) _2 (SCN) _2] The calculated results show that the complexation of NO_3 ~ -, H_2O and SCN ~ - with Co (Ⅱ) complexes is a photochemical one.