Co-ordination chemistry of octamethyl-5,5′-di(2-pyridyl)ferrocene[hair space]

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Beate Neumann, Ulrich Siemeling, Hans-Georg Stammler, Udo Vorfeld, Johannes G. P. Delis, Piet W. N. M. van Leeuwen, Kees Vrieze, Jan Fraanje, Kees Goubitz, Fabrizia Fabrizi de Biani and Piero Zanello


Abstract

The platinum complex [{PtCl2(C2H4)}2(dpf[hair space]*) 1 [dpf[hair space]* = octamethyl-5,5′-di(2-pyridyl)ferrocene] has been obtained by the reaction of dpf[hair space]* with K[PtCl3(C2H4)]. The reaction of dpf[hair space]* with [Cu(NCCH3)4]+[BF4] afforded the copper complexes [Cu(dpf[hair space]*)]+ [BF4]2 and [Cu(dpf[hair space]*)]+[CuCl2]3 as well as the ferrocenium salt [dpf[hair space]*]+[BF4]4, depending on the stoichiometry. The crystal structures of 14 have been determined by X-ray diffraction. The dpf[hair space]* acts as a bridging ligand in the case of 1 and as a trans-chelating ligand in 2 and 3, which contain near-linear two-co-ordinate copper centres. Complex 3 shows a remarkably short, ligand-unsupported CuI[hair space]· · ·[hair space][hair space]CuI contact [281.0(2) pm]. A cyclovoltammetric study of 2 revealed an unprecedentedly high anodic shift of the half-wave potential of the ferrocene moiety upon co-ordination of Cu+ by dpf[hair space]*.


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