Trilacunary A-beta-Keggin tungstogermanates and -silicates functionalized with phenyltin(IV) electrophiles.
The first organic derivative of a beta-Keggin tungstogermanate, the monomeric Keggin anion [{(C(6)H(5))Sn(OH)}(3)(A-beta-GeW(9)O(34))](4-) (1), was the only species isolated from the reaction of (C(6)H(5))SnCl(3) with Na(10)[A-beta-GeW(9)O(34)] in water, whereas the Si-analogue [{(C(6)H(5))Sn(OH)}(3)(A-beta-SiW(9)O(34))](4-) (2) and two dimeric tungstosilicates, the unprecedented species [{(C(6)H(5))Sn(A-beta-H(3)SiW(9)Sn(2)O(37))}(2)O(2)](8-) (3) and the known sandwich-type polyanion [{(C(6)H(5))Sn(OH)}(3)(A-beta-H(3)SiW(9)O(34))(2)](8-) (4), were isolated starting from [A-beta-SiW(9)O(34)](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 ((1)H, (13)C, (117)Sn, and (183)W) and solid-state (117)Sn CP-MAS NMR study enabled full characterization of 1. A weak 1-dimensional polyanion association through (Sn)O-HO(t) hydrogen contacts involving one of the protonated bridging O atoms of the (C(6)H(5))(3)Sn(3)O(12) corner-shared triad is observed for 1 by X-ray diffraction, resulting in a local C(s) pseudosymmetry for the Sn centers detected by solid-state (117)Sn NMR spectroscopy.
Reinoso
Santiago
S
School of Engineering and Science, Jacobs University, P. O. Box 750 561, 28725, Bremen, Germany.
Piedra-Garza
Luis Fernando
LF
Dickman
Michael H
MH
Praetorius
Antonia
A
Biesemans
Monique
M
Willem
Rudolph
R
Kortz
Ulrich
U
D005857:Germanium / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D015394:Molecular Structure; D009947:Organotin Compounds / Q000737:chemistry*; D000071228:Polyelectrolytes; D011108:Polymers / Q000737:chemistry*; D017640:Silicates / Q000737:chemistry*; D013055:Spectrophotometry, Infrared; D017973:Tungsten Compounds / Q000138:chemical synthesis / Q000737:chemistry*
D005857:Germanium; D009947:Organotin Compounds; D000071228:Polyelectrolytes; D011108:Polymers; D017640:Silicates; D017973:Tungsten Compounds; C063613:phenyltin