Condensation of N-(2-hydroxyethyl)ethylenediamine and pyridine-2-carbaldehyde in the presence of ZnX₂ salts (X = ClO₄⁻, Cl⁻, Br⁻, I⁻) generates four complexes, namely, [ZnL1Cl](ClO₄) (1), [ZnL1Cl][ZnCl₃(H₂O)]·2H₂O (2), [ZnL1Br][ZnBr₃(H₂O)]·2H₂O (3), and [Zn(L2)₃]I₂ (4), where L1 and L2 are aminal and hemiaminal ether derivatives, i.e., (E)-N-((pyridine-2-yl)methylene)-2-((2-pyridine-2-yl)oxazolidin-3-yl)ethanamine and 2-(2-pyridin-2-yl-imidazolidin-1-yl)-ethanol, respectively. No complex with the expected Schiff-base ligand (E)-2-(2-(pyridin-2-ylmethyleneamino)ethylamino)ethanol (L) or with 2-(2-pyridyl-3-(2-hydroxyethyl))oxazolidine (L3) was obtained. The structures of complexes 1, 3, and 4 have been elucidated by single crystal X-ray diffraction. All the complexes have been characterized by detailed NMR (¹H, ¹³C and DEPT-135) and ESI-MS analyses, indicating retention of solid state structures in the solution phase. Complex 1 deserves special mention as during its formation, the ClO₄⁻ ion undergoes reduction to Cl⁻ and thus, it forms a mixed anionic ligand complex. Thorough DFT calculations have been performed at the BP86-D3/def2-TZVP level of theory to rationalize the ligand and complex formation. The calculations suggest that the aminal form (L1) is the most favored species followed by the Schiff-base, whereas the hemiaminal ether form (L3) is the least preferred one. The role of halides during the formation of the monoanionic [ZnX₃(H₂O)]⁻ species is crucial, and the achieved complex is highly favored when X = Cl and disfavored for X = I; this trend has been rationalized by the DFT calculations. The phosphatase activities of the complexes have been investigated, and their efficiencies follow the order 2 > 1 > 3 > 4.

中文翻译：

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具有不常见的氨基和半氨基醚衍生物的 锌（ii）配合物：合成，结构，磷酸酶活性以及配体和配合物形成的理论合理性†

的缩合ñ - （2-羟乙基）乙二胺和吡啶-2-甲醛在ZNX存在₂盐（X = CLO ₄ ^- ，氯^- ，溴^- ，我^- ）产生四个配合物，即，[ZnL1Cl]（CLO ₄）（1），[ZnL1Cl] [ZnCl ₃（H ₂ O）]·2H ₂ O（2），[ZnL1Br] [ZnBr ₃（H ₂ O）]·2H ₂ O（3）和[Zn（ L2）₃ ] I ₂（4），其中L1和L2是氨基和半氨基醚衍生物，即，（E）-N -（（吡啶-2-基）亚甲基）-2-（（2-吡啶-2-基）恶唑烷丁-3-基）乙胺和2-（2-吡啶-2-基-分别为咪唑烷基-1-基）-乙醇。与预期的席夫碱配体（E）-2-（2-（吡啶-2-基亚甲基氨基）乙基氨基）乙醇（L）或与2-（2-吡啶基-3-（2-羟乙基））恶唑烷（获得L3）。复合物的结构1，3和4已经通过单晶X射线衍射阐明。所有配合物均已通过详细的NMR（¹ H，¹³ C和DEPT-135）和ESI-MS分析进行了表征，表明固相结构保留在溶液相中。综合大楼1值得作为其形成过程中，所述CLO特别提到₄ ^-离子经受还原成氯^-并且因此，它形成了一个混合阴离子配位体配合物。在BP86-D3 / def2-TZVP的理论水平上已进行了彻底的DFT计算，以使配体和配合物形成合理化。计算表明，氨醛形式（L1）是最受青睐的物种，其次是席夫碱，而半胱氨酸醚形式（L3）是最不受欢迎的物种。卤化物在单阴离子[ZnX ₃（H ₂ O）] ^-形成过程中的作用物种是至关重要的，当X = Cl时，所获得的络合物极受青睐，而对于X = I时，则不利。通过DFT计算已经合理化了这种趋势。研究了复合物的磷酸酶活性，其效率遵循2 > 1 > 3 > 4的顺序。