Macrocyclic diorganotin complexes of gamma-amino acid dithiocarbamates as hosts for ion-pair recognition.
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).
Centro de Investigaciones Quimicas, Universidad Autonoma del Estado de Morelos, Av. Universidad 1001, C.P. 62209 Cuernavaca, Mexico.
Jorge
J
Cruz-Huerta
Manuel
M
Carillo-Morales
Ericka
E
Santacruz-Juárez
Irán F
IF
Hernández-Ahuactzi
Jaime
J
Escalante-García
Carolina
C
Godoy-Alcantar
Jorge A
JA
Guerrero-Alvarez
Herbert
H
Höpfl
Hugo
H
Morales-Rojas
Mario
M
Sánchez
D000596:Amino Acids / Q000737:chemistry*; D000838:Anions / Q000737:chemistry; D002412:Cations / Q000737:chemistry; D018360:Crystallography, X-Ray; D057927:Hydrophobic and Hydrophilic Interactions; D008024:Ligands; D047028:Macrocyclic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D009947:Organotin Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D013055:Spectrophotometry, Infrared; D013818:Thermogravimetry; D013859:Thiocarbamates / Q000138:chemical synthesis / Q000737:chemistry*
D000596:Amino Acids; D000838:Anions; D002412:Cations; D008024:Ligands; D047028:Macrocyclic Compounds; D009947:Organotin Compounds; D013859:Thiocarbamates; C056189:di-n-butyltin; C063612:diphenyltin