Ferrocene-Functionalized Cu(I)/Ag(I) Dithiocarbamate Clusters
Ferrocene-Functionalized Cu(I)/Ag(I) Dithiocarbamate Clusters
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DOI：
10.1021/acs.inorgchem.6b00201
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发表时间：
2016-04-04
影响因子：
4.6
通讯作者：
Liu, C. W.
中科院分区：
文献类型：
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作者：
Kishore, Pilli V. V. N.;Liao, Jian-Hong;Liu, C. W.
合成了一系列化合物，即[Cu-8(mu(4)-H){S(2)CNMeCH(2)Fc}(6)](PF6) (1), [Cu-7(mu(4)-H) {S(2)CN(i)PrCH(2)Fc}(6)] (2), [Cu-3{S2CN(Bz) (CH(2)Fc)}(2)(dppf)(2)](PF6)(3)和[Ag-2{S2CNMe(CH(2)Fc)}2(PPh3)(2)] （4) （dppf = 1,1'-双（二苯基膦）二茂铁）），由多二茂铁组合支撑。所有化合物均通过H-1 NMR、傅里叶变换红外、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是一个单阳离子的八核Cu-I簇，2是一个中性的七核Cu-I簇，具有四捕获四面体(1)和三捕获四面体(2)的几何形状，被间隙氢化物包裹，在核心的外围由六个二茂铁单元锚定。化合物3和4包含由四个和两个二茂铁基团包裹的三金属Cu-I和双金属Ag-I核。有趣的是，在3中观察到dppf配体的螯合和桥接结合模式。进一步证明了多羟基铜簇[Cu28H15{S(2)CN(i)PrCH(2)Fc}(12)](PF6)(5)和[Cu28H15{(S2CNBu2)-Bu-n}(12)](PF6)(7)的形成和分离，它们由笨重的二茂铁和正丁基二硫氨基甲酸酯配体稳定。它们很容易通过H-2 NMR在它们的氘类似物[Cu28D15{S(2)CN(i)PrCH(2)Fc}(12)](PF6)(6)和[Cu28D15{(S2CNBu2)-Bu-n}(12)](PF6)(8)上进行鉴定。虽然化合物5的结构细节和光谱表征还有待研究，但化合物7可以通过包括单晶x射线衍射在内的各种光谱进行充分表征。化合物1、2和4的循环伏安研究显示Fe2+/Fe3+对的不可逆氧化还原峰，其中由于配合物在电极表面的一些吸附，还原峰不能很好地分解。
A series of compounds, namely, [Cu-8(mu(4)-H){S(2)CNMeCH(2)Fc}(6)](PF6) (1), [Cu-7(mu(4)-H) {S(2)CN(i)PrCH(2)Fc}(6)] (2), [Cu-3{S2CN(Bz) (CH(2)Fc)}(2)(dppf)(2)](PF6) (3), and [Ag-2{S2CNMe(CH(2)Fc)}2(PPh3)(2)] (4) (dppf = 1,1'-bis(diphenylphosphino)ferrocene), supported by multiferrocene assemblies, were synthesized. All the compounds were characterized by H-1 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{S(2)CN(i)PrCH(2)Fc}(12)](PF6) (5) and [Cu28H15{(S2CNBu2)-Bu-n}(12)](PF6) (7), stabilized by bulky ferrocenyl and n-butyl dithiocarbamate ligands, was demonstrated. They are readily identified by H-2 NMR studies on their deuterium analogues, [Cu28D15{S(2)CN(i)PrCH(2)Fc}(12)](PF6) (6) and [Cu28D15{(S2CNBu2)-Bu-n}(12)](PF6) (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 Fe2+/Fe3+ couple wherein the reduction peaks are not well-resolved due to some adsorption of the complex onto the electrode surface.