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Mahrholdt, Julia
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article
Isocyano- and cyanoferrocenes in the synthesis of palladium, gold and zinc complexes
Abstract
<p>The reaction of 2 equiv. of FcN[tbnd]C (2) or FcC[tbnd]N (4) with [PdCl<sub>2</sub>(cod)] (1) in boiling toluene gave cis-[PdCl<sub>2</sub>(C[tbnd]NFc)<sub>2</sub>] (3) and cis-[PdCl<sub>2</sub>(N[tbnd]CFc)<sub>2</sub>] (5), respectively (cod = cycloocta-1,5-diene; Fc = Fe(ƞ<sup>5</sup>-C<sub>5</sub>H<sub>4</sub>)(ƞ<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)). Treatment of 4 with ZnBr<sub>2</sub> (6) in a 2:1 stoichiometry produced [ZnBr<sub>2</sub>(N[tbnd]CFc)<sub>2</sub>] (7), while 2 and [AuCl(SMe<sub>2</sub>)] (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 C<sub>5</sub>H<sub>4</sub> 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.</p>