title: Synthesis and structure of dawson polyoxometalate-based, multifunctional, inorganic-organic hybrid compounds: organogermyl complexes with one terminal functional group and organosilyl analogues with two terminal functional groups.
abstract: Four novel multifunctional polyoxometalate (POM)-based inorganic-organic hybrid compounds, [α(2)-P(2)W(17)O(61){(RGe)}](7-) (Ge-1, R(1) = HOOC(CH(2))(2(-)) and Ge-2, R(2) = H(2)C═CHCH(2(-))) and [α(2)-P(2)W(17)O(61){(RSi)(2)O}](6-) (Si-1, R(1) and Si-2, R(2)), were prepared by incorporating organic chains having terminal functional groups (carboxylic acid and allyl groups) into monolacunary site of Dawson polyoxoanion [α(2)-P(2)W(17)O(61)](10-). In these POMs, new modification of the terminal functional groups was attained by introducing organogermyl and organosilyl groups. Dimethylammonium salts of the organogermyl complexes, (Me(2)NH(2))(7)[α(2)-P(2)W(17)O(61)(R(1)Ge)]·H(2)O MeN-Ge-1 and (Me(2)NH(2))(7)[α(2)-P(2)W(17)O(61)(R(2)Ge)]·4H(2)O MeN-Ge-2, were obtained as analytically pure crystals, in 22.8% and 55.3% yields, respectively, by stoichiometric reactions of [α(2)-P(2)W(17)O(61)](10-) with separately prepared Cl(3)GeC(2)H(4)COOH in water, and H(2)C═CHCH(2)GeCl(3) in a solvent mixture of water/acetonitrile. Synthesis and X-ray structure analysis of the Dawson POM-based organogermyl complexes were first successful. Dimethylammonium salts of the corresponding organosilyl complexes, (Me(2)NH(2))(6)[α(2)-P(2)W(17)O(61){(R(1)Si)(2)O}]·4H(2)O MeN-Si-1 and (Me(2)NH(2))(6)[α(2)-P(2)W(17)O(61){(R(2)Si)(2)O}]·6H(2)O MeN-Si-2, were also obtained as analytically pure crystalline crystals, in 17.1% and 63.5% yields, respectively, by stoichiometric reactions of [α(2)-P(2)W(17)O(61)](10-) with NaOOC(CH(2))(2)Si(OH)(2)(ONa) and H(2)C═CHCH(2)Si(OEt)(3). These complexes were characterized by elemental analysis, thermogravimetric and differential thermal analyses (TG/DTA), FTIR, solid-state ((31)P) and solution ((31)P, (1)H, and (13)C) NMR, and X-ray crystallography.
authors: Department of Chemistry, Faculty of Science, Kanagawa University, Hiratsuka, Kanagawa 259-1293, Japan. nomiya@kanagawa-u.ac.jp
authors: Kenji
authors: K
authors: Nomiya
authors: Yoshihiro
authors: Y
authors: Togashi
authors: Yuhki
authors: Y
authors: Kasahara
authors: Shotaro
authors: S
authors: Aoki
authors: Hideaki
authors: H
authors: Seki
authors: Marie
authors: M
authors: Noguchi
authors: Shoko
authors: S
authors: Yoshida
mesh_terms: D018360:Crystallography, X-Ray; D005857:Germanium / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D017646:Organosilicon Compounds / Q000737:chemistry*; D017550:Spectroscopy, Fourier Transform Infrared; D013818:Thermogravimetry; D017973:Tungsten Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D000099294:Polyoxometalates
chemical_list: D005857:Germanium; D009942:Organometallic Compounds; D017646:Organosilicon Compounds; D017973:Tungsten Compounds; C102296:polyoxometalate I; D000099294:Polyoxometalates