Novel polymeric aggregates of pentaphosphaferrocenes and monocationic coinage metal salts - Synthesis of [{Cp*Fe (η5-P5)}{Cu(GaCl4)}2]n and [{CpBIGFe(η5-P5)}Ag]n [Al(OC(CF3)3)4]n

The reaction of pentaphosphaferrocenes [(CpFe)-Fe-R(eta(5)-P-5)] (CPR = Cp* = eta(5)-C5Me5, Cp-BIG = eta(5)-C-5(4-(BuC6H4)-Bu-n)) with monocationic salts of copper and silver leads to the formation of [{Cp*Fe(eta(5)-P-5)}{Cu(GaCl4)}(2)](n) (2) and [{(CpFe)-Fe-BIG(n(5)-P-5)}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. (C) 2014 Elsevier B.V. All rights reserved.