Abstract
The reaction of pentaphosphaferrocenes [CpRFe(η5-P5)] (CpR=Cp∗=η5-C5Me5, CpBIG=η5-C5(4-nBuC6H4)) with monocationic salts of copper and silver leads to the formation of [{Cp∗Fe(η5-P5)}{Cu(GaCl4)}2]n (2) and [{CpBIGFe(η5-P5)}Ag]n[Al{OC(CF3)3}4]n (3), respectively, representing the rare structural motifs of a 1,2,3,4- or a 1,3-coordination mode of the cyclo-P5 unit. Both the 2D network as well as the 1D polymer are obtained from self-assembly processes and characterized by X-ray structure analysis. Compound 2 exemplifies a sheet-like structure, whose layers are linked by short Cl⋯H-contacts, whereas the structure of 3 is comprised of cationic strands, whose positive charge is balanced by the weakly coordinating anion [Al{OC(CF3)3}4]. Dissociative properties of both polymeric complexes are compared by solution and solid state NMR spectroscopy.
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