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

Hakikulla H. Shah, Rayya A. Al-Balushi, Mohammed K. Al-Suti, Muhammad S. Khan, Frank Marken, Anna L. Sudlow, Gabriele Kociok-Köhn, Christopher H. Woodall, Paul R. Raithby, Kieran C. Molloy

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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 "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 2, 3, and 4, respectively, indicating the presence of two [PF 6]- 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.

Original languageEnglish
Pages (from-to)9497-9507
Number of pages11
JournalDalton Transactions
Issue number25
Publication statusPublished - Jul 7 2014


ASJC Scopus subject areas

  • Inorganic Chemistry

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