Kishore Pilli V V N, Liao Jian-Hong, Hou Hsing-Nan, Lin Yan-Ru, Liu C W
Department of Chemistry, National Dong Hwa University , Hualien, Taiwan 97401, R. O. C.
Inorg Chem. 2016 Apr 4;55(7):3663-73. doi: 10.1021/acs.inorgchem.6b00201. Epub 2016 Mar 24.
A series of compounds, namely, Cu8(μ4-H){S2CNMeCH2Fc}6 (1), [Cu7(μ4-H) {S2CN(i)PrCH2Fc}6] (2), Cu3{S2CN(Bz) (CH2Fc)}2(dppf)2 (3), and [Ag2{S2CNMe(CH2Fc)}2(PPh3)2] (4) (dppf = 1,1'-bis(diphenylphosphino)ferrocene), supported by multiferrocene assemblies, were synthesized. All the compounds were characterized by (1)H NMR, Fourier transform infrared, elemental analysis, and electrospray ionization mass spectrometry techniques. Single-crystal X-ray structural analysis revealed that 1 is a monocationic octanuclear Cu(I) cluster and that 2 is a neutral heptanuclear Cu(I) cluster with tetracapped tetrahedral (1) and tricapped tetrahedral (2) geometries entrapped with an interstitial hydride, anchored by six ferrocene units at the periphery of the core. Compounds 3 and 4 comprise trimetallic Cu(I) and dimetallic Ag(I) cores enfolded by four and two ferrocene moieties. Interestingly both chelating and bridging modes of binding are observed for dppf ligand in 3. Further the formation and isolation of polyhydrido copper clusters Cu28H15{S2CN(i)PrCH2Fc}12 (5) and Cu28H15{S2CN(n)Bu2}12 (7), stabilized by bulky ferrocenyl and n-butyl dithiocarbamate ligands, was demonstrated. They are readily identified by (2)H NMR studies on their deuterium analogues, Cu28D15{S2CN(i)PrCH2Fc}12 (6) and Cu28D15{S2CN(n)Bu2}12 (8). Though the structure details as well as spectroscopic characterizations of 5 are yet to be investigated, the compound 7 is fully characterized by variety of spectroscopy including single-crystal X-ray diffraction. The cyclic voltammetry studies for compounds 1, 2, and 4 display irreversible redox peaks for Fe(2+)/Fe(3+) couple wherein the reduction peaks are not well-resolved due to some adsorption of the complex onto the electrode surface.
合成了一系列由多二茂铁组装体支撑的化合物，即Cu8(μ4-H){S2CNMeCH2Fc}6 (1)、[Cu7(μ4-H){S2CN(i)PrCH2Fc}6] (2)、Cu3{S2CN(Bz)(CH2Fc)}2(dppf)2 (3) 和 [Ag2{S2CNMe(CH2Fc)}2(PPh3)2] (4)（dppf = 1,1'-双（二苯基膦基）二茂铁）。所有化合物均通过1H NMR、傅里叶变换红外光谱、元素分析和电喷雾电离质谱技术进行了表征。单晶X射线结构分析表明，1是一个单阳离子八核Cu(I)簇，2是一个中性七核Cu(I)簇，具有嵌入间隙氢化物的四帽四面体(1)和三帽四面体(2)几何结构，由六个二茂铁单元锚定在核心外围。化合物3和4包含由四个和两个二茂铁部分包裹的三金属Cu(I)和二金属Ag(I)核心。有趣的是，在3中观察到dppf配体的螯合和桥连结合模式。此外，还证明了由庞大的二茂铁基和正丁基二硫代氨基甲酸盐配体稳定的多氢铜簇Cu28H15{S2CN(i)PrCH2Fc}12 (5)和Cu28H15{S2CN(n)Bu2}12 (7)的形成和分离。通过对它们的氘类似物Cu28D15{S2CN(i)PrCH2Fc}12 (6)和Cu28D15{S2CN(n)Bu2}12 (8)的2H NMR研究很容易识别它们。尽管5的结构细节和光谱表征尚未研究，但化合物7已通过包括单晶X射线衍射在内的各种光谱进行了全面表征。化合物1、2和4的循环伏安研究显示Fe(2+)/Fe(3+)电对的不可逆氧化还原峰，其中还原峰由于配合物在电极表面的一些吸附而分辨不清。
