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首页> 外文期刊>Polyhedron: The International Journal for Inorganic and Organometallic Chemistry >Co(III) complexes of the type [(L)Co(O2CO)](+) (L = tripodal tetraamine ligand): Synthesis, structure, DFT calculations and Co-59 NMR
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Co(III) complexes of the type [(L)Co(O2CO)](+) (L = tripodal tetraamine ligand): Synthesis, structure, DFT calculations and Co-59 NMR

机译：[（L）Co（O2CO）]（+）类型的Co（III）配合物（L =三脚架四胺配体）：合成，结构，DFT计算和Co-59 NMR

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摘要

The syntheses and characterisation of the Co(III) complexes [(L)Co(O2CO)]ClO4 (L = a tripodal tetraamine ligand = baep, abap, uns-penp, dppa, trpn) are reported. Geometric isomers are possible for all but the trpn complex, owing to the non-equivalence of the three arms on the tripodal ligand, and both NMR and X-ray crystallography are used to identify the single isomer formed. X-ray crystal structures of the complexes [(L)Co(O2CO)]ClO4 center dot xH(2)O (L = baep, x = 0.5; L = abap, x = 0; L = uns-penp, x = 1; L = dppa, x = 0; L = trpn, x = 1) are reported; little variation is observed in the geometry of the carbonate chelate ring while significant lengthening of bonds and expansion of angles involving the cobalt ion occurs as the number of six-membered chelate rings in the complex cations increases. Co-59 NMR chemical shift data for the complexes show the expected linear relationship between lambda(max), the wavelength of the lowest energy d-d transition, and gamma, the magnetogyric ratio of the Co-59 nucleus. An excellent correlation between Delta, the d orbital splitting parameter, and delta(Co-59) also exists for these complexes. Rate data for the acid hydrolysis of [(L)Co(O2CO)](+) (L = uns-penp, dppa) in 1.0 M HClO4 differ by two orders of magnitude, and this is attributed to the differing steric accessibility of the endo O atoms in each complex. DFT calculations on the complexes reproduce the isomeric preferences, UV-Vis and Co-59 NMR spectroscopic data well, provided that solvent effects are included.
机译：报道了Co（III）配合物[（L）Co（O2CO）] ClO4（L =三脚架四胺配体= baep，abap，uns-penp，dppa，trpn）的合成和表征。由于三脚架配体上三个臂的不等价性，除trpn络合物外，所有异构体都可能存在几何异构体，并且NMR和X射线晶体学都用于鉴定形成的单一异构体。配合物[（L）Co（O2CO）] ClO4中心点xH（2）O的X射线晶体结构（L =哔哔声，x = 0.5; L = apap，x = 0; L = uns-penp，x = 1; L = dppa，x = 0; L = trpn，x = 1）被报告;碳酸盐螯合环的几何形状几乎没有变化，而随着络合阳离子中六元螯合环数量的增加，键的显着延长和涉及钴离子的夹角会发生扩展。配合物的Co-59 NMR化学位移数据显示了lambda（max）（最低能量d-d跃迁的波长）和γ（Co-59核的磁电比）之间的预期线性关系。对于这些复合物，Δ，d轨道分裂参数和delta（Co-59）之间也存在极好的相关性。 [（L）Co（O2CO）]（+）（L = uns-penp，dppa）在1.0 M HClO4中的酸水解速率数据相差两个数量级，这归因于每个配合物中的O原子。如果考虑到溶剂效应，则对配合物的DFT计算可以很好地再现异构体偏好，UV-Vis和Co-59 NMR光谱数据。

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