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Dalton Transactions

The international journal for inorganic, organometallic and bioinorganic chemistry



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Dalton Trans., 2010, 39, 248 - 255, DOI: 10.1039/b910889k

Trilacunary A--Keggin tungstogermanates and -silicates functionalized with phenyltin(IV) electrophiles

Santiago Reinoso, Luis Fernando Piedra-Garza, Michael H. Dickman, Antonia Praetorius, Monique Biesemans, Rudolph Willem and Ulrich Kortz

The first organic derivative of a -Keggin tungstogermanate, the monomeric Keggin anion [{(C6H5)Sn(OH)}3(A--GeW9O34)]4- ( 1), was the only species isolated from the reaction of (C6H5)SnCl3 with Na10[A--GeW9O34] in water, whereas the Si-analogue [{(C6H5)Sn(OH)}3(A--SiW9O34)]4- ( 2) and two dimeric tungstosilicates, the unprecedented species [{(C6H5)Sn(A--H3SiW9Sn2O37)}2O2]8- ( 3) and the known sandwich-type polyanion [{(C6H5)Sn(OH)}3(A--H3SiW9O34)2]8- ( 4), were isolated starting from [A--SiW9O34]10-. The novel polyanion 3 can be described as the product of a double Sn–C hydrolysis followed by condensation of two subunits of 2 through double Sn–O–Sn bridge formation. Solid-state characterization has been carried out by infrared spectroscopy, thermogravimetry and single-crystal X-ray diffraction, representing the first structural analysis for 4. A full solution multinuclear NMR (1H, 13C, 117Sn, and 183W) and solid-state 117Sn CP-MAS NMR study enabled full characterization of 1. A weak 1-dimensional polyanion association through (Sn)O–HOt hydrogen contacts involving one of the protonated bridging O atoms of the (C6H5)3Sn3O12 corner-shared triad is observed for 1 by X-ray diffraction, resulting in a local Cs pseudosymmetry for the Sn centers detected by solid-state 117Sn NMR spectroscopy.

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