Matsuki Yusuke, Hoshino Takahiro, Takaku Shoko, Matsunaga Satoshi, Nomiya Kenji
Department of Chemistry, Faculty of Science, Kanagawa University , Hiratsuka, Kanagawa 259-1293, Japan.
Inorg Chem. 2015 Dec 7;54(23):11105-13. doi: 10.1021/acs.inorgchem.5b01206. Epub 2015 Nov 13.
A novel trititanium(IV)-substituted Wells-Dawson polyoxometalate (POM)-based organometallic complex, i.e., a dimeric POM containing two bridging CpRh(2+) groups (Cp = C5Me5) or {α-P2W15Ti3O60(OH)2}2(Cp*Rh)2 (D-1) with Ci symmetry, was synthesized in an analytically pure form by a 1:2 -molar ratio reaction of the organometallic precursor [CpRhCl2]2 with the separately prepared, monomeric trititanium(IV)-substituted Wells-Dawson POM, "P2W15Ti3O59(OH)3" (M-1). The crystalline sample (NaK-D-1) of the water-soluble, mixed sodium/potassium salt of D-1 was obtained in the 14.7% yield, which has been characterized by complete elemental analysis, TG/DTA, FTIR, single-crystal X-ray structure analysis, and solution ((183)W, (31)P, (1)H and (13)C{(1)H}) NMR spectroscopy. Single-crystal X-ray structure analysis revealed that the two species of the protonated Wells-Dawson subunits, "P2W15Ti3O60(OH)2" were bridged by the two CpRh(2+) groups, resulting in the an overall Ci symmetry. The Cp*Rh(2+) groups were linked to the two terminal oxygen atoms of the titanium(IV) sites and one edge-sharing oxygen atom of the surface Ti-O-Ti bond. The (183)W NMR of D-1 dissolved in D2O showed that its solution structure was represented as a dimeric POM with a formula of {α-P2W15Ti3O60(OH)3}2{Cp*Rh(OH)}2 (D-2) with Ci (or S2) symmetry. A trititanium(IV)-substituted Wells-Dawson POM-supported organometallic complex has never been reported so far, and thus D-1 in the solid state and D-2 in solution are the first example of this type of complex.
一种新型的三钛（IV）取代的韦尔斯-道森多金属氧酸盐（POM）基有机金属配合物，即一种含有两个桥连CpRh(2+)基团（Cp = C5Me5）的二聚体POM，或{α-P2W15Ti3O60(OH)2}2(Cp*Rh)2（D-1），具有Ci对称性，通过有机金属前体[CpRhCl2]2与单独制备的单体三钛（IV）取代的韦尔斯-道森POM“P2W15Ti3O59(OH)3”（M-1）以1:2的摩尔比反应，以分析纯形式合成。水溶性的D-1的混合钠/钾盐的晶体样品（NaK-D-1）以14.7%的产率获得，已通过完整的元素分析、TG/DTA、FTIR、单晶X射线结构分析和溶液（(183)W、(31)P、(1)H和(13)C{(1)H}）NMR光谱进行了表征。单晶X射线结构分析表明，两种质子化的韦尔斯-道森亚基“P2W15Ti3O60(OH)2”通过两个CpRh(2+)基团桥连，从而产生整体的Ci对称性。Cp*Rh(2+)基团与钛（IV）位点的两个末端氧原子以及表面Ti-O-Ti键的一个共边氧原子相连。溶解在D2O中的D-1的(183)W NMR表明，其溶液结构表示为具有Ci（或S2）对称性的二聚体POM，化学式为{α-P2W15Ti3O60(OH)3}2{Cp*Rh(OH)}2（D-2）。迄今为止，尚未报道过三钛（IV）取代的韦尔斯-道森POM负载的有机金属配合物，因此固态的D-1和溶液中的D-2是这类配合物的第一个例子。
