Abstract
Two new dinuclear diorganotin(IV) dithiocarbamate (dtc) macrocycles, [Me2Sn(dtc)]2 (1) and [nBu2Sn(dtc)]2 (2), have been synthesized from R2SnCl2 (R = Me, nBu) and the bis(dithiocarbamate) derivative of N,N -dibenzylhexamethylene-1,6-diamine. These complexes have been characterized by elemental analysis, FAB mass spectrometry, IR and NMR (H, C, Sn) spectroscopy, as well as single crystal X-ray crystallography. The dtc ligands are coordinated to the tin atoms in the anisobidentate manner, both in solution and the solid state. The metal centers are hexacoordinated and the coordination polyhedron of the tin atoms can be described as bicapped tetrahedron or skew trapezoidal bipyramid. The cavities of the 26-membered macrocycles are hydrophobic with four sulfur atoms directed into the interior and have an inner diameter of approximately 4.1 x 5.6 A. The crystal structure of [Me2Sn(dtc)]2 (1) is stabilized by the presence of two chloroform molecules per asymmetric unit, which participate in intermolecular C-H⋅⋅⋅S, C-H⋅⋅⋅Cl hydrogen bonding and S⋅⋅⋅Cl donor acceptor interactions. On the other hand, the crystal structure of [nBu2Sn(dtc]2 (2) is stabilized additionally by intermolecular C-H⋅⋅⋅π interactions.
Highlights
During the last few years the metal ion directed self assembly of ligands to well-defined structures has been exploited mainly in two directions: first, the generation of discrete cyclooligomeric molecular structures having cavities and, second, the creation of microporous coordination polymers.[1]
In this contribution we present an extension of this strategy to the synthesis of diorganotin(IV) dithiocarbamate macrocycles, the results of which are presented
One-pot syntheses from this amine, carbon disulfide, triethylamine and R2SnCl2 (R = Me, nBu) gave colorless precipitates that were recrystallized from chloroform and a mixture of dichloromethane/methanol to give the dinuclear diorganotin(IV) dithiocarbamate macrocycles, [Me2Sn(dtc)]2 (1) and [nBu2Sn(dtc]2 (2), in yields of 54 and 36 %, respectively (Scheme 1)
Summary
During the last few years the metal ion directed self assembly of ligands to well-defined structures has been exploited mainly in two directions: first, the generation of discrete cyclooligomeric molecular structures having cavities and, second, the creation of microporous coordination polymers.[1]. Synthetic Methods The secondary diamine, N,N-dibenzylhexamethylene-1,6-diamine, used as starting material for the preparation of the diorganotin complexes, was obtained in 90% yield by condensation of benzaldehyde with 1,6-hexamethylenediamine in ethanol followed by reduction of the Schiff base with NaBH4 in methanol.[6] One-pot syntheses from this amine, carbon disulfide, triethylamine and R2SnCl2 (R = Me, nBu) gave colorless precipitates that were recrystallized from chloroform and a mixture of dichloromethane/methanol to give the dinuclear diorganotin(IV) dithiocarbamate macrocycles, [Me2Sn(dtc)]2 (1) and [nBu2Sn(dtc]2 (2), in yields of 54 and 36 %, respectively (Scheme 1).
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