Synthesis, electrochemical and theoretical studies of the Au(I)-Cu(I) heterometallic clusters bearing ferrocenyl groups

Igor O. Koshevoy*, Ekaterina S. Smirnova, Antonio Domenech, Antti J. Karttunen, Matti Haukka, Sergey P. Tunik, Tapani A. Pakkanen

*Corresponding author for this work

Research output: Contribution to journalArticleScientificpeer-review

Abstract

Treatment of the polymeric alkynyl compounds (AuC(2)R)(n) (R = Fc, C(6)H(4)Fc; Fc = ferrocenyl) with the diphosphine PPh(2)C(6)H(4)PPh(2) gave complexes (RC(2)Au)PPh(2)C(6)H(4)PPh(2)(AuC(2)R) (1, R = Fc; 2, R = C(6)H(4)Fc) with end-capped ferrocenyl groups. The reactions of 1 or 2 with Cu(NCMe)(4)PF(6) result in formation of the heterotrimetallic aggregates [{Au(3)Cu(2)(C(2)R)(6)} Au(3)(PPh(2)C(6)H(4)PPh(2))(3)](PF(6))(2) (3, R = Fc; 4, R = C(6)H(4)Fc), which consist of the alkynyl clusters [Au(3)Cu(2)(C(2)R)(6)](-) "wrapped" by the cationic [Au(3)(PPh(2)C(6)H(4)PPh(2))(3)](3+) "belt". The novel compounds were characterized by NMR spectroscopy and ESI-MS measurements. The solid state structure of 3 is reported. Electrochemical properties of the complexes 1 - 4 have been studied. These data show that all six ferrocenyl units are oxidized in the clusters 3 and 4. The Fc groups of 3 are electronically coupled into each other, but in 4 behave essentially independently. Electronic structure calculations have been performed, showing good correlation with the X-ray and electrochemical studies.

Original languageEnglish
Pages (from-to)8392-8398
Number of pages7
JournalDalton Transactions
Issue number39
DOIs
Publication statusPublished - 2009
MoE publication typeA1 Journal article-refereed

Keywords

  • APPROXIMATE COULOMB POTENTIALS
  • TRANSITION-METAL-COMPLEXES
  • AUXILIARY BASIS-SETS
  • ELECTRONIC DELOCALIZATION
  • CU-I
  • GOLD
  • ENERGY
  • BEHAVIOR
  • LIGANDS
  • DESIGN

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