Cruz-Huerta Jorge, Carillo-Morales Manuel, Santacruz-Juárez Ericka, Hernández-Ahuactzi Irán F, Escalante-García Jaime, Godoy-Alcantar Carolina, Guerrero-Alvarez Jorge A, Höpfl Herbert, Morales-Rojas Hugo, Sánchez Mario
Centro de Investigaciones Quimicas, Universidad Autonoma del Estado de Morelos, Av. Universidad 1001, C.P. 62209 Cuernavaca, Mexico.
Inorg Chem. 2008 Nov 3;47(21):9874-85. doi: 10.1021/ic8007987. Epub 2008 Oct 8.
The dimethyl-, di-n-butyl-, and diphenyltin(IV) dithiocarbamate (dtc) complexes [{R2Sn(L-dtc)}x] 1-7 (1, L = L1, R = Me; 2, L = L1, R = n-Bu; 3, L = L2, R = Me, x = infinity; 4, L = L2, R = n-Bu; 5, L = L3, R = Me, x = 2; 6, L = L3, R = n-Bu, x = 2; 7, L = L3, R = Ph, x = 2) have been prepared from a series of secondary amino acid (AA) homologues as starting materials: N-benzylglycine (alpha-AA derivative = L1), N-benzyl-3-aminopropionic acid (beta-AA derivative = L2), and N-benzyl-4-aminobutyric acid (gamma-AA derivative = L3). The resulting compounds have been characterized by elemental analysis, mass spectrometry, IR and NMR ((1)H, (13)C, and (119)Sn) spectroscopy, thermogravimetric analysis, and X-ray crystallography, showing that in all complexes both functional groups of the heteroleptic ligands are coordinated to the tin atoms. By X-ray diffraction analysis, it could be shown that [{Me2Sn(L2-dtc)}x] (3) is polymeric in the solid state, while the complexes derived from L3 (5-7) have dinuclear 18-membered macrocyclic structures of the composition [{R2Sn(L3-dtc)}2]. For the remaining compounds, it could not be established with certainty whether the structures are macrocyclic or polymeric. A theoretical investigation at the B3LYP/SBKJC(d,p) level of theory indicated that the alpha-AA-dtc complexes might have trinuclear macrocyclic structures. The macrocyclic complexes 5-7 have a double-calix-shaped conformation with two cavities large enough for the inclusion of aliphatic and aromatic guest molecules. They are self-complementary for the formation of supramolecuar synthons that give rise to 1D molecular arrangements in the solid state. Preliminary recognition experiments with tetrabutylammonium acetate have shown that the [{R2Sn(L3-dtc)}2] macrocycles 6 and 7 might interact simultaneously with anions (AcO(-)), which coordinate to the tin atoms, and organic cations (TBA(+)), which accommodate within the hydrophobic cavity (ion-pair recognition).
二甲基、二正丁基和二苯基锡（IV）二硫代氨基甲酸盐（dtc）配合物[{R2Sn（L-dtc）}] 1-7（1，L = L1，R = 甲基；2，L = L1，R = 正丁基；3，L = L2，R = 甲基，x = ∞；4，L = L2，R = 正丁基；5，L = L3，R = 甲基，x = 2；6，L = L3，R = 正丁基，x = 2；7，L = L3，R = 苯基，x = 2）由一系列仲氨基酸（AA）同系物作为起始原料制备而成：N-苄基甘氨酸（α-AA衍生物 = L1）、N-苄基-3-氨基丙酸（β-AA衍生物 = L2）和N-苄基-4-氨基丁酸（γ-AA衍生物 = L3）。所得化合物通过元素分析、质谱、红外光谱和核磁共振（（1）H、（13）C和（119）Sn）光谱、热重分析和X射线晶体学进行了表征，结果表明在所有配合物中，杂配体的两个官能团均与锡原子配位。通过X射线衍射分析可知，[{Me2Sn（L2-dtc）}]x（3）在固态下为聚合物，而源自L3的配合物（5-7）具有组成式为[{R2Sn（L3-dtc）}]2的双核18元大环结构。对于其余化合物，无法确定其结构是大环结构还是聚合物结构。在B3LYP/SBKJC（d，p）理论水平上的理论研究表明，α-AA-dtc配合物可能具有三核大环结构。大环配合物5-7具有双杯状构象，有两个足够大的空腔可容纳脂肪族和芳香族客体分子。它们在形成超分子合成子方面具有自互补性，从而在固态下产生一维分子排列。用醋酸四丁铵进行的初步识别实验表明，[{R2Sn（L3-dtc）}]2大环化合物6和7可能同时与阴离子（AcO（-））相互作用，阴离子与锡原子配位，还与有机阳离子（TBA（+））相互作用，有机阳离子容纳在疏水空腔内（离子对识别）。
