Centro de Química Estrutural, Complexo I, Instituto Superior Técnico, TU Lisbon, Av. Rovisco Pais, 1049-001, Lisbon, Portugal.
Dalton Trans. 2011 May 21;40(19):5352-61. doi: 10.1039/c0dt01457e. Epub 2011 Apr 4.
The zinc(II) complexes with ortho-hydroxy substituted arylhydrazo-β-diketonates [Zn(2)(CH(3)OH)(2)(μ-L(1))(2)] (5), [Zn{(CH(3))(2)SO}(H(2)O)(L(2))] (6), [Zn(2)(H(2)O)(2)(μ-L(3))(2)] (7) and [Zn(H(2)O)(2)(L(4))]·H(2)O (8) were synthesized by reaction of a zinc(II) salt with the appropriate hydrazo-β-diketone, HO-2-C(6)H(4)-NHN=C{C(=O)CH(3)}(2) (H(2)L(1), 1), HO-2-O(2)N-4-C(6)H(3)-NHN=C{C(=O)CH(3)}(2) (H(2)L(2), 2), HO-2-C(6)H(4)-NHN=CC(=O)CH(2)C(CH(3))(2)CH(2)C(=O) (H(2)L(3), 3) or HO-2-O(2)N-4-C(6)H(3)-NHN=[CC(=O)CH(2)C(CH(3))(2)CH(2)C(=O) (H(2)L(4), 4). They were fully characterized, namely by X-ray diffraction analysis that disclosed the formation of extensive H-bonds leading to 1D chains (5 and 6), 2D layers (7) or 3D networks (8). The thermodynamic parameters of the Zn(II) reaction with H(2)L(2) in solution, as well as of the thermal decomposition of 1-8 were determined. Complexes 5-8 act as diastereoselective catalysts for the nitroaldol (Henry) reaction. The threo/erythro diastereoselectivity of the β-nitroalkanol products ranges from 8:1 to 1:10 with typical yields of 80-99%, depending on the catalyst and substrate used.
锌（II）与邻位羟基取代芳基腙-β-二酮配合物 [Zn(2)(CH(3)OH)(2)(μ-L(1))(2)] (5)、[Zn{(CH(3))(2)SO}(H(2)O)(L(2))] (6)、[Zn(2)(H(2)O)(2)(μ-L(3))(2)] (7) 和 [Zn(H(2)O)(2)(L(4))]·H(2)O (8) 是通过锌（II）盐与适当的腙-β-二酮反应合成的，HO-2-C(6)H(4)-NHN=C{C(=O)CH(3)}(2) (H(2)L(1), 1)、HO-2-O(2)N-4-C(6)H(3)-NHN=C{C(=O)CH(3)}(2) (H(2)L(2), 2)、HO-2-C(6)H(4)-NHN=CC(=O)CH(2)C(CH(3))(2)CH(2)C(=O) (H(2)L(3), 3) 或 HO-2-O(2)N-4-C(6)H(3)-NHN=[CC(=O)CH(2)C(CH(3))(2)CH(2)C(=O) (H(2)L(4), 4)。它们通过 X 射线衍射分析得到了充分的表征，该分析揭示了形成广泛的 H 键，导致一维链（5 和 6）、二维层（7）或三维网络（8）。还确定了锌（II）与 H(2)L(2)在溶液中的反应以及 1-8 的热分解的热力学参数。配合物 5-8 作为硝基醇醛（Henry）反应的非对映选择性催化剂。β-硝基醇产物的 threo/erythro 非对映选择性范围为 8:1 至 1:10，产率典型为 80-99%，具体取决于所用的催化剂和底物。
