Synthesis and Characterization of Dimolybdenum(II) Complexes Connected by Carboxylate Linkers

The dinuclear complex cis-[(CH3CN)6Mo2(O2C-Fc)2(BF4)2] (2) and the square-shaped compound [(CH3CN)4Mo2(O2C-Fc-CO2)­(BF4)2]4 (3) can be synthesized by reacting [Mo2(NCCH3)10]­[BF4]4 (1) with the corresponding ferrocenemonocarboxylic and -dicarboxylic acids (FMCA and FDCA) in a mixture of CH3CN and THF. The reaction of [Mo2(NCCH3)10] [BF4]4 (1) with tetrafluoroterephthalic acid in propionitrile solution affords the square-shaped complex [(CH3CH2CN)4Mo2(O2C-C6F4-CO2)­(BF4)2]4 (4). The interaction of 1 with 5-fluoroisophthalic acid using acetonitrile as solvent results in the isolation of the triangular complex [(CH3CN)6Mo2(m-bdc-F)(BF4)2]3 (5). The products 2–5 have been characterized by single-crystal X-ray diffraction, NMR spectroscopy (1H, 11B, 13C, 19F), IR spectroscopy, elemental analysis, TG-MS, and UV–vis spectroscopy measurements.

双核顺式配合物[(CH3CN)6Mo2(O2C-Fc)2(BF4)2] (2) 与方形结构化合物[(CH3CN)4Mo2(O2C-Fc-CO2)(BF4)2]4 (3)，可通过将[Mo2(NCCH3)10][BF4]4 (1) 与相应的二茂铁单羧酸(ferrocenemonocarboxylic acid, FMCA)、二茂铁二羧酸(ferrocenedicarboxylic acid, FDCA)在乙腈与四氢呋喃的混合溶剂中反应制得。将[Mo2(NCCH3)10][BF4]4 (1) 与四氟对苯二甲酸在丙腈溶剂中反应，可得到方形结构配合物[(CH3CH2CN)4Mo2(O2C-C6F4-CO2)(BF4)2]4 (4)。以乙腈为溶剂，将1与5-氟间苯二甲酸反应，可分离得到三角形配合物[(CH3CN)6Mo2(m-bdc-F)(BF4)2]3 (5)。产物2~5均通过单晶X射线衍射、核磁共振（1H、11B、13C、19F）波谱、红外光谱、元素分析、热重-质谱联用（TG-MS）以及紫外-可见（UV–vis）分光光度法完成表征。