Bis[di‐n‐alkyl(fluoro)stannyl]methanes, (R₂FSn)₂CH₂ (R = n‐octyl, n‐dodecyl): Stable Fluoride‐Selective Carriers

Abstract

The synthesis of bis[di‐n‐alkyl(fluoro)stannyl]methanes, [(R2)FSn]2CH2, (3, R = n‐octyl; 4, R = n‐dodecyl), is reported and their unprecedented dimeric structure in solution with pentacoordinate tin atoms is rationalized on the basis of 19F and 119Sn NMR spectroscopy, osmometric molecular mass determination and electrospray mass spectrometry (ESMS). 19F and 119Sn MAS NMR and Mössbauer spectroscopy also indicate pentacoordinate tin atoms for the solid state. The ability of compounds 3 and 4 to bind fluoride ion selectively and reversibly is evaluated through potentiometric measurements. Compared with the previously reported organotin(IV)‐based fluoride ionophore [Cl(Ph2)Sn]2CH2, 3 and 4 exhibit a drastically improved lifetime, while retaining their high preference for fluoride over all other lipophilic anions evaluated. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

Organotin‐Substituted Crown Ethers for Ditopic Complexation of Anions and Cations

“…However, an essential shortcoming of the latter compounds is the kinetic lability of the tin-carboxylate bond, which makes the corresponding zwitterionic complexes unstable in solution. [18b] In continuation of our own studies on organotin halides as Lewis acids for selective complexation of anions [21][22][23] we report here the synthesis and structures of kinetically more stable carbon-bonded organotin-functionalized crown ethers and demonstrate that such compounds are able to complex and transport sodium rhodanide in nonpolar organic solvents.…”

Double-C,N-chelated tri- and diorganotin(IV) fluorides

“…The compounds have fivecoordinated tin and are able to fluorinate titanocene dichloride essentialy quantitatively. Latest reports on this field deals with triorganotin fluorides of Me 3 SnF [11] and (R 2 FSn) 2 CH 2 type, where the second type of compound was studied as stable fluoride-selective carriers [12]. The X-ray based studies of complex difluorotriorganostannates [Ph 3 SnF 2 ] À [13] and [(Ph 2 FSn) 2 CH 2 F] À [14] appeared as well.…”

Solubilizing Sodium Fluoride in Acetonitrile: Synthesis, Molecular Structure, and Complexation Behavior of Bis(organostannyl)methyl‐Substituted Crown Ethers

“…[18] Linking such a bis(organostannyl)methane moiety to an appropriate sodium-cation-specific crown ether should enhance the chance of charge separation by ditopic complexation of sodium fluoride.…”