abstract
4',4"'-Bis(ferrocenyl)-2,2':6',2'':6",2'":6'",2-''"-quinquepyridine(Fc(2)qpy)reacts with AgOTf (OTf = trifluoromethylsulfonate) to give a complex of stoichiometry [Ag(Fc2qpy)]OTf. The crystal structure reveals a dinuclear arrangement among the cations with an (AgAg)-Ag-... close contact of 3.089(2) A. The ligands are wrapped around the silver atoms in a double helical array. Further hydrogen bonding between triflate units and the protons of the ferrocene or pyridine moieties results in a supramolecular structure. Theoretical studies confirm the existence of a weak Ag-Ag bond, and show that the dinuclear form can be more stable than the mononuclear one, when there is a favorable balance between the reorganization energy of the two quinquepyridine chains and the energy released by the formation of stronger Ag-N bonds and the new Ag-Ag interaction in the helix, ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004).
keywords
STATE-INDUCED TRANSFORMATIONS; DENSITY-FUNCTIONAL THEORY; EFFECTIVE CORE POTENTIALS; RAY CRYSTAL-STRUCTURE; MOLECULAR-STRUCTURES; 2,2'/6',2''/6'',2'''/6''',2''''-QUINQUEPYRIDINE QPY; INORGANIC COMPLEXES; RUTHENIUM COMPLEXES; METALLOSUPRAMOLECULAR CHEMISTRY; NUMERICAL-INTEGRATION
subject category
Chemistry
authors
Aguado, JE; Calhorda, MJ; Costa, PJ; Crespo, O; Felix, V; Gimeno, MC; Jones, PG; Laguna, A
our authors
Paulo Jorge Ferreira de Matos Costa
Post-doc Fellowship