New di-ferrocenyl-ethynylpyridinyl triphenylphosphine copper halide complexes and related di-ferricenyl electro-crystallized materials

作者：Shah Hakikulla H; Al Balushi Rayya A; Al Suti Mohammed K; Khan Muhammad S^*; Marken Frank; Sudlow Anna L; Kociok Koehn Gabriele; Woodall Christopher H; Raithby Paul R; Molloy Kieran C

来源：Dalton Transactions, 2014, 43(25): 9497-9507.

DOI：10.1039/c3dt52914b

Three new neutral di-ferrocenyl-ethynylpyridinyl copper complexes, [L-2(CuCl)(2)(PPh3)(2)] (2), [L-2(CuBr)(2)(PPh3)(2)] (3), and [L-2(CuI)(2)(PPh3)(2)] (4)were synthesized from the ferrocenyl-ethynylpyridine ligand (L)(1), 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 %26quot;stripping reduction peaks%26quot; 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 2, 3, and 4, respectively, indicating the presence of two [PF6]-anions in the vicinity of the dioxidized complexes, and suggesting product formulae [2](2+)[PF6](2)(-), [3](2+)[PF6](2)(-) and [4](2+)[PF6](2)(-)

• 出版日期2014