Issue 13, 2004

Organotin and organogermanium linkers for simple, direct functionalization of polyoxotungstates

Abstract

Fifteen Keggin-anion-derived polytungstates [TW11O39{MCH2CH2X}]n (T = Si, Ge, Ga; M = Sn, Ge; X = COOH, COOCH3, CONH2, CN; n = 5, 6) were prepared in aqueous or aqueous–organic solution from the corresponding lacunary polytungstates and trichlorotin and –germanium precursors, and were isolated as caesium salts. The derivatized polytungstates were characterized by elemental analysis, multinuclear NMR spectroscopy, and cyclic voltammetry; they are stable in aqueous solution to pH 6–7. NMR spectroscopy revealed the presence of a second (β1 or β3) isomer in the tungstogallate derivatives. Acid hydrolysis of the ester and nitrile derivatives could be achieved without decomposition of the polytungstate moieties, and esterification and amidation of the carboxylate functions was straightforward using standard coupling techniques, e.g. the formation, isolation and characterization of [SiW11O39{Ge(CH2)2CONHCH2COOCH3}]5− from glycine methyl ester. Since the Cl3MCH2CH2X precursors are readily accessible by hydrostannation/germanation reactions with the corresponding alkenes, novel coupled polytungstates, such as [(SiW11O39GeCH2CH2COOCH2)4C]20− from pentaerythritol tetraacrylate, can also be prepared.

Graphical abstract: Organotin and organogermanium linkers for simple, direct functionalization of polyoxotungstates

Article information

Article type
Paper
Submitted
28 Apr 2004
Accepted
17 May 2004
First published
28 May 2004

Dalton Trans., 2004, 1989-1994

Organotin and organogermanium linkers for simple, direct functionalization of polyoxotungstates

G. Sazani and M. T. Pope, Dalton Trans., 2004, 1989 DOI: 10.1039/B402421D

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