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

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• 作者：Ericka Santacruz-Juá ; rez ; Jorge Cruz-Huerta ; Irá ; n Fernando Herná ; ndez-Ahuactzi ; Reyna Reyes-Martí ; nez ; Hugo Tlahuext ; Hugo Morales-Rojas ; Herbert Hö ; pfl
• 刊名：Inorganic Chemistry
• 出版年：2008
• 出版时间：November 3, 2008
• 年：2008
• 卷：47
• 期：21
• 页码：9804-9812
• 全文大小：333K
• 年卷期：v.47,no.21(November 3, 2008)
• ISSN：1520-510X

文摘

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-ⁱBu-ambdtc), 1,4-bis(benzylaminomethyl)benzene (1,4-Bn-ambdtc), and 1,4-bis(iso-butylaminomethyl)benzene (1,4-ⁱBu-ambdtc) were reacted with three different diorganotin dichlorides (R₂SnCl₂ with R = Me, ⁿBu, 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 (¹H, ¹³C, and ¹¹⁹Sn) 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 ¹¹⁹Sn 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-ⁱBu-ambdtc, 1,4-Bn-ambdtc, and 1,1′-Bn-amfdtc and the di-n-butyltin derivative of 1,3-ⁱBu-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-ⁱBu-ambdtc, the metal centers have distorted octahedral coordination with symmetrically coordinating cis-oriented dtc functions. Thus, for the complexes derived from 1,3-Bn/ⁱBu-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 occurr, which differ in the spatial orientation of the substituents attached to the nitrogen atoms (Bn or ⁱBu). The dimethyltin derivatives of 1,4-Bn-ambdtc and 1,1′-Bn-amfdtc have cavities, in which aromatic rings are accomodated in the solid state.