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Synthesis and ligand properties towards gold and silver of the ferrocenylamidobenzimidazole ligand
Authors:Maria José Calhorda  Paulo J Costa  Paulo N Martinho  M Concepción Gimeno  Antonio Laguna  M Dolores Villacampa
Institution:a Instituto de Tecnologia Química e Biológica (ITQB), Av. da República, EAN, Apt 127, 2781-901 Oeiras, Portugal
b Departamento de Química e Bioquímica, Faculdade de Ciências da Universidade de Lisboa, 1749-016 Lisboa, Portugal
c Departamento de Química Inorgánica, Instituto de Ciencia de Materiales de Aragón, Universidad de Zaragoza-CSIC, E-50009 Zaragoza, Spain
Abstract:The treatment of FcCOCl (Fc = (C5H5)Fe(C5H4)) with aminobenzimidazole in 1:1 or 2:1 ratio gives the ferrocenyl-amido derivatives FcCO(benzimNH2) or (FcCO)2(NHbenzim), respectively. The reactivity of FcCO(benzimNH2) with silver or gold complexes has been studied. The reaction with the basic gold compounds Au(acac)(PPh3)] or O(AuPPh3)3]ClO4 occurs with deprotonation of the NH2 group and coordination of one or three gold(phosphine) fragments. The treatment of this ligand with silver compounds, such as Ag(OTf) or Ag(OTf)(PPh3)], gives the complexes of stoichiometry Ag(OTf)L] or Ag(OTf)(PPh3)L]. The ligand FcCO(benzimNH2) and the complex Ag(OTf){FcCO(benzimNH2)}(PPh3)] have been characterized by X-ray diffraction studies. DFT calculations were performed on models of this dimeric silver complex and showed that dimerization is energetically favourable, because Ag(I) achieves a four coordination environment, despite some bonds being relatively weak.
Keywords:Gold  Silver  Ferrocene derivatives  DFT calculations  Azolate ligands
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