New di-ferrocenyl-ethynylpyridinyl triphenylphosphine copper halide complexes and related di-ferricenyl electro-crystallized materials.
New di-ferrocenyl-ethynylpyridinyl triphenylphosphine copper halide complexes and related di-ferricenyl electro-crystallized materials.
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DOI：
10.1039/c3dt52914b
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发表时间：
2014-06
影响因子：
4
通讯作者：
Hakikulla H. Shah;Rayya A. Al-Balushi;Mohammed K. Al-Suti;Muhammad S. Khan;F. Marken;A. Sudlow;G. Kociok‐Köhn;C. H. Woodall;P. Raithby;K. Molloy
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文献类型：
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作者：
Hakikulla H. Shah;Rayya A. Al-Balushi;Mohammed K. Al-Suti;Muhammad S. Khan;F. Marken;A. Sudlow;G. Kociok‐Köhn;C. H. Woodall;P. Raithby;K. Molloy
以二茂铁乙炔基吡啶配体（L）（）、适当的卤化铜CuX（X = Cl（-），Br（-），I（-））和三苯基膦为原料，合成了三个新的中性双二茂铁乙炔基吡啶铜配合物[L2（CuCl）2（PPh 3）2]（），[L2（CuBr）2（PPh 3）2]（）和[L2（CuI）2（PPh 3）2]（）.这些中性配合物的光谱方法和单晶X-射线晶体学充分其特征在于。循环伏安法在二氯乙烷中揭示了化学可逆的二茂铁基氧化信号，随后是特征性的“剥离还原峰”，显示了氧化产物电结晶的证据。扫描电子显微镜证实自发形成的结晶氧化产物具有三种不同的形态X = Cl（-），Br（-），I（-）。能量色散X射线元素分析数据显示Fe：P比为1：2.0、1：2.1和1：2.0。2.1对于络合物的电结晶产物，和，分别表明在二氧化络合物附近存在两个[PF 6]（-）阴离子，并提出产物式[]（2+）[PF 6]（-）2，[]（2+）[PF 6]（-）2和[]（2+）[PF 6]（-）2。
Three new neutral di-ferrocenyl-ethynylpyridinyl copper complexes, [L2(CuCl)2(PPh3)2] (), [L2(CuBr)2(PPh3)2] (), and [L2(CuI)2(PPh3)2] () were synthesized from the ferrocenyl-ethynylpyridine ligand (L) (), the appropriate copper halide CuX (with X = Cl(-), Br(-), I(-)) and triphenylphosphine. These neutral complexes were fully characterized by spectroscopic methods and by single crystal X-ray crystallography. Cyclic voltammetry in dichloroethane revealed chemically reversible ferrocenyl oxidation signals followed by characteristic "stripping reduction peaks" showing evidence for oxidation-product electro-crystallization. Scanning electron microscopy confirmed spontaneous formation of crystalline oxidation products with three distinct morphologies for X = Cl(-), Br(-), I(-). Energy dispersive X-ray elemental analysis data show Fe : P ratios of 1 : 2.0, 1 : 2.1 and 1 : 2.1 for electro-crystallization products of complexes , , and , respectively, indicating the presence of two [PF6](-) anions in the vicinity of the dioxidized complexes, and suggesting product formulae [](2+)[PF6](-)2, [](2+)[PF6](-)2 and [](2+)[PF6](-)2.