Department of Chemistry, Faculty of Science, Kanagawa University, Hiratsuka, Kanagawa 259-1293, Japan.
Inorg Chem. 2011 Oct 3;50(19):9606-19. doi: 10.1021/ic201336v. Epub 2011 Sep 8.
Four novel multifunctional polyoxometalate (POM)-based inorganic-organic hybrid compounds, α(2)-P(2)W(17)O(61){(RGe)} (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} (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). 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) 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) 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.
四种新型多功能多金属氧酸盐（POM）基无机-有机杂化化合物，α(2)-P(2)W(17)O(61){(RGe)}（Ge-1，R(1) = HOOC(CH(2))(2(-)) 和 Ge-2，R(2) = H(2)C═CHCH(2(-)))和α(2)-P(2)W(17)O(61){(RSi)(2)O}（Si-1，R(1)和 Si-2，R(2)），是通过将具有末端官能团（羧酸和烯丙基）的有机链引入 Dawson 多酸阴离子α(2)-P(2)W(17)O(61)的单缺位位来制备的。在这些 POM 中，通过引入有机锗基和有机硅基来实现末端官能团的新修饰。有机锗配合物的二甲铵盐，（Me(2)NH(2))(7)[α(2)-P(2)W(17)O(61)(R(1)Ge)]·H(2)O MeN-Ge-1 和（Me(2)NH(2))(7)[α(2)-P(2)W(17)O(61)(R(2)Ge)]·4H(2)O MeN-Ge-2，分别通过α(2)-P(2)W(17)O(61)与分别制备的 Cl(3)GeC(2)H(4)COOH 在水中和 H(2)C═CHCH(2)GeCl(3)在水/乙腈的混合溶剂中的化学计量反应，以分析纯晶体的形式获得，产率分别为 22.8%和 55.3%。 Dawson POM 基有机锗配合物的合成和 X 射线结构分析首次成功。相应的有机硅配合物的二甲铵盐，（Me(2)NH(2))(6)[α(2)-P(2)W(17)O(61){(R(1)Si)(2)O}]·4H(2)O MeN-Si-1 和（Me(2)NH(2))(6)[α(2)-P(2)W(17)O(61){(R(2)Si)(2)O}]·6H(2)O MeN-Si-2，也通过α(2)-P(2)W(17)O(61)与 NaOOC(CH(2))(2)Si(OH)(2)(ONa)和 H(2)C═CHCH(2)Si(OEt)(3)的化学计量反应，以分析纯晶体的形式获得，产率分别为 17.1%和 63.5%。这些配合物通过元素分析、热重和差热分析（TG/DTA）、FTIR、固态（(31)P）和溶液（(31)P、(1)H 和(13)C）NMR 和 X 射线晶体学进行了表征。
