Centro de Química Estrutural, Complexo I, Instituto Superior Técnico, Technical University of Lisbon, Av. Rovisco Pais, 1049-001 Lisbon, Portugal.
Chemistry. 2013 Jan 7;19(2):588-600. doi: 10.1002/chem.201203254. Epub 2012 Nov 23.
A one-pot template condensation of 2-(2-(dicyanomethylene)hydrazinyl)benzenesulfonic acid (H(2)L(1), 1) or 2-(2-(dicyanomethylene)hydrazinyl)benzoic acid (H(2)L(2), 2) with methanol (a), ethylenediamine (b), ethanol (c) or water (d) on copper(II), led to a variety of metal complexes, that is, mononuclear [Cu(H(2)O)(2)(κO(1),κN(2)L(1a)] (3) and [Cu(H(2)O)(κO(1),κN(3)L(1b))] (4), tetranuclear [Cu(4)(1κO(1),κN(2):2κO(1)L(2a))(3)-(1κO(1), κN(2):2κO(2)L(2a))] (5), Cu(2)(H(2)O)(1κO(1), κN(2):2κO(1)L(2c))-(1κO(1),1κN(2):2κO(1),2 κN(1)- L(2c)) (6) and Cu(2)(H(2)O)(2)(κO(1),κN(2)- L(1dd))-(1κO(1),κN(2):2κO(1)L(1dd))(μ-H(2)O) 2H(2)O (7·2H(2)O), as well as polymer- ic Cu(H(2)O)(κO(1),1κN(2):2κN(1)L(1c)) (8) and Cu(NH(2)C(2)H(5))(κO(1),1κN(2):2κN(1)L(2a)) (9). The ligands 2-SO(3)H-C(6)H(4)-(NH)N=C{(CN)[C(NH(2))-(=NCH(2)CH(2)NH(2))]} (H(2)L(1b), 10), 2-CO(2)H-C(6)H(4)-(NH)N={C(CN)[C(OCH(3))-(=NH)]} (H(2)L(2a), 11) and 2-SO(3)H-C(6)H(4)-(NH)N=C{C(=O)-(NH(2))}(2) (H(2)L(1dd), 12) were easily liberated upon respective treatment of 4, 5 and 7 with HCl, whereas the formation of cyclic zwitterionic amidine 2-(SO(3)(−))-C(6)H(4)-N=NC(-C=(NH(+))CH(2)CH(2)NH)(=CNHCH(2)CH(2)NH) (13) was observed when 1 was treated with ethylenediamine. The hydrogen bond-induced E/Z isomerization of the (HL(1d))(−) ligand occurs upon conversion of {Na(H(2)O)(2)(μ-H(2)O)(2)}(HL(1d)) (14) to [Cu(H(2)O)(6)]HL(1d)·2H(2)O (15) and [{CuNa(H(2)O)-(κN(1),1κO(2):2κO(1)L(1d))(2)}K(0.5)(μ-O)(2)]n·H(2)O (16). The synthesized complexes 3–9 are catalyst precursors for both the selective oxidation of primary and secondary alcohols (to the corresponding carbonyl compounds) and the following diastereoselective nitroaldol (Henry) reaction, with typical yields of 80–99%.
一锅模板缩合 2-(2-(二氰基亚甲基)肼基)苯磺酸 (H(2)L(1), 1) 或 2-(2-(二氰基亚甲基)肼基)苯甲酸 (H(2)L(2), 2) 与甲醇 (a)、乙二胺 (b)、乙醇 (c) 或水 (d) 在铜(II)上，导致各种金属配合物的形成，即单核 [Cu(H(2)O)(2)(κO(1),κN(2)L(1a)] (3) 和 [Cu(H(2)O)(κO(1),κN(3)L(1b))] (4)、四核 [Cu(4)(1κO(1),κN(2):2κO(1)L(2a))(3)-(1κO(1), κN(2):2κO(2)L(2a))] (5)、Cu(2)(H(2)O)(1κO(1), κN(2):2κO(1)L(2c))-(1κO(1),1κN(2):2κO(1),2 κN(1)-L(2c)) (6) 和 Cu(2)(H(2)O)(2)(κO(1),κN(2)-L(1dd))-(1κO(1),κN(2):2κO(1)L(1dd))(μ-H(2)O) 2H(2)O (7·2H(2)O)，以及聚合物 Cu(H(2)O)(κO(1),1κN(2):2κN(1)L(1c)) (8) 和 Cu(NH(2)C(2)H(5))(κO(1),1κN(2):2κN(1)L(2a)) (9)。配体 2-SO(3)H-C(6)H(4)-(NH)N=C{(CN)[C(NH(2))-(=NCH(2)CH(2)NH(2))]} (H(2)L(1b), 10)、2-CO(2)H-C(6)H(4)-(NH)N={C(CN)[C(OCH(3))-(=NH)]} (H(2)L(2a), 11) 和 2-SO(3)H-C(6)H(4)-(NH)N=C{C(=O)-(NH(2))}(2) (H(2)L(1dd), 12) 分别与 HCl 反应时很容易释放出来，而当 1 与乙二胺反应时，观察到环状两性离子脒 2-(SO(3)(−))-C(6)H(4)-N=NC(-C=(NH(+))CH(2)CH(2)NH)(=CNHCH(2)CH(2)NH) (13) 的形成。(HL(1d))(−)配体的氢键诱导 E/Z 异构化发生在 {Na(H(2)O)(2)(μ-H(2)O)(2)}(HL(1d)) (14) 转化为 [Cu(H(2)O)(6)]HL(1d)·2H(2)O (15) 和 [{CuNa(H(2)O)-(κN(1),1κO(2):2κO(1)L(1d))(2)}K(0.5)(μ-O)(2)]n·H(2)O (16) 时。合成的配合物 3-9 是两种选择性氧化伯醇和仲醇（转化为相应的羰基化合物）以及随后的非对映选择性硝基醇醛（Henry）反应的催化剂前体，典型收率为 80-99%。
