Isocyano- and cyanoferrocenes in the synthesis of palladium, gold and zinc complexes

Julia Mahrholdt, Julian Noll, Marcus Korb, Tobias Rüffer, Heinrich Lang

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The reaction of 2 equiv. of FcN[tbnd]C (2) or FcC[tbnd]N (4) with [PdCl2(cod)] (1) in boiling toluene gave cis-[PdCl2(C[tbnd]NFc)2] (3) and cis-[PdCl2(N[tbnd]CFc)2] (5), respectively (cod = cycloocta-1,5-diene; Fc = Fe(ƞ5-C5H4)(ƞ5-C5H5)). Treatment of 4 with ZnBr2 (6) in a 2:1 stoichiometry produced [ZnBr2(N[tbnd]CFc)2] (7), while 2 and [AuCl(SMe2)] (8) in a 1:1 M ratio gave [AuCl(C[tbnd]NFc)] (9). The molecular structures of 3, 5, 7 and 9 in the solid state were determined by single crystal X-ray structure analysis. Gold complex 9 shows aurophilic interactions that, together with parallel displaced π···π contacts between C5H4 entities, form a linear coordination polymer along [1 1 0]. Cyclic voltammetry studies confirm that the Fc groups in 3, 5, 7 and 9 are reversibly oxidized at 435 mV (3), 445 mV (5), 445 mV (7) and 545 mV (9). Coordination of 2 towards Pd(II) or Au(I) shifts the redox potential significantly from 355 mV to 435 mV (3) or 545 mV (9). Contrary, complexation of 4 (450 mV) to Pd(II) or Zn(II) hardly affects the ferrocenyl-related redox potentials.

Original languageEnglish
Article number120829
JournalInorganica Chimica Acta
Publication statusPublished - 1 May 2022


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