24- and 26-Membered Macrocyclic Diorganotin(IV) Bis-Dithiocarbamate Complexes withN,N′-Disubstituted 1,3- and 1,4-Bis(aminomethyl)benzene and 1,1′-Bis(aminomethyl)ferrocene as Spacer Groups

Abstract

The potassium bis-dithiocarbamate (bis-dtc) salts of 1,3-bis(benzylaminomethyl)benzene (1,3-Bn-ambdtc), 1,3-bis(iso-butylaminomethyl)benzene (1,3-(i)Bu-ambdtc), 1,4-bis(benzylaminomethyl)benzene (1,4-Bn-ambdtc), and 1,4-bis(iso-butylaminomethyl)benzene (1,4-(i)Bu-ambdtc) were reacted with three different diorganotin dichlorides (R2SnCl2 with R = Me, (n)Bu, and Ph) in 1:1 stoichiometric ratios to give the corresponding diorganotin bis-dithiocarbamates. Additionally, the dimethyltin bis-dithiocarbamate of 1,1'-bis(benzylaminomethyl)ferrocene (1,1'-Bn-amfdtc) was prepared. The resulting complexes have been characterized as far as possible by elemental analysis, FAB(+) mass spectrometry, IR and NMR ((1)H, (13)C, and (119)Sn) spectroscopy, and single-crystal X-ray diffraction, showing that the tin complexes are dinuclear 24- and 26-membered macrocyclic species of composition [{R2Sn(bis-dtc)}2]. As shown by (119)Sn NMR spectroscopy, the tin centers are hexa-coordinated in all cases; however, two different coordination environments are possible, as detected by single-crystal X-ray diffraction. In the dimethyltin derivatives of 1,3-Bn-ambdtc, 1,3-(i)Bu-ambdtc, 1,4-Bn-ambdtc, and 1,1'-Bn-amfdtc and the di-n-butyltin derivative of 1,3-(i)Bu-ambdtc, the metal atoms are embedded in skewed-trapezoidal-bipyramidal coordination polyhedra with asymmetrically coordinating trans-oriented dtc groups. In contrast, in the diphenyltin derivative 1,3-(i)Bu-ambdtc, the metal centers have distorted octahedral coordination with symmetrically coordinating cis-oriented dtc functions. Thus, for the complexes derived from 1,3-Bn/(i)Bu-ambdtc, two different macrocyclic structures were observed. In the dimethyl- and di-n-butyltin derivatives, the bridging bis-dtc ligands adopt U-shaped conformations, while in the case of the diphenyltin derivative, the conformation is L-shaped. Furthermore, two different macrocyclic ring conformations can occur, which differ in the spatial orientation of the substituents attached to the nitrogen atoms (Bn or (i)Bu). The dimethyltin derivatives of 1,4-Bn-ambdtc and 1,1'-Bn-amfdtc have cavities, in which aromatic rings are accommodated in the solid state.

Synthesis, Structure, and Fungicidal Activity of Organotin Dithiocarbamates Derived from Pyridinamines and Aryl Diamines

“…Figure shows that two bis‐dithiocarbamate ligands coordinate to two tin centers in an anisobidentate manner to form a 20‐membered macrocyclic structure in 11 . Each tin atom has a skewed‐trapezoidal bipyramidal coordination geometry, similar to previously reported macrocyclic diorganotin bis‐dithiocarbamates . The pyridyl nitrogen atoms do not still participate in the coordination, like those in 1 and 7 .…”

“…Recently, the multifunctional dithiocarbamate ligands, such as dithiocarbamates with additional donor atoms and bridging bis‐ and tris‐ dithiocarbamate ligands, have been used for the construction of high nuclearity organotin aggregates; some of which showed good molecular recognition function for anionic and neutral species . A number of macrocyclic and cagelike organotin dithiocarbamates have been synthesized by this strategy. It is known that small modifications to the ligand can lead to significant changes in the coordination geometry of the tin atom in complexes as well as their bioactivities.…”

Triorganotin(IV) derivatives with semirigid heteroditopic hydroxo‐carboxylato ligands: Synthesis, characterization, and cytotoxic properties

“…In combination with linear‐shaped metal‐complex tectons, U‐shaped ligands can give rise to either [2 + 2] macrocyclic or [n + n] polymeric supramolecular assemblies. [ 14–16 ] In the crystal structures of compounds 4 and 8 – 10 , 1D coordination polymers with alternate upside‐down orientation of the ligand molecules are observed (Figures 7 and 8). Interestingly, albeit having the same ligand‐to‐metal connectivity, compounds 5 and 6 have [2 + 2] macrocyclic structures, which are discussed in the following section.…”

Synthesis, spectra, crystal structures and anticancer studies of 26‐membered macrocyclic dibutyltin(IV) dithiocarbamate complexes: Single‐source precursors for tin sulfide nanoparticles

“…In some cases, diorganotin(IV) derivatives have also shown acceptable in vivo antiproliferative activity as new chemotherapy agents . In addition, these complexes have been found to be efficient and somewhat selective anion and cation receptors . Recently, investigations in the field of photovoltaics have been directed towards the development of cost‐effective and non‐toxic materials for solar cell fabrication.…”