Abstract
Solid-gas reactions and in situ powder X-ray diffraction investigations of trinuclear silver complexes {[3,4,5-(CF(3))(3)Pz]Ag}(3) and {[4-Br-3,5-(CF(3))(2)Pz]Ag}(3) supported by highly fluorinated pyrazolates reveal that they undergo intricate ethylene-triggered structural transformations in the solid-state producing dinuclear silver-ethylene adducts. Despite the complexity, the chemistry is reversible producing precursor trimers with the loss of ethylene. Less reactive {[3,5-(CF(3))(2)Pz]Ag}(3) under ethylene pressure and low-temperature conditions stops at an unusual silver-ethylene complex in the trinuclear state, which could serve as a model for intermediates likely present in more common trimer-dimer reorganizations described above. Complete structural data of three novel silver-ethylene complexes are presented together with a thorough computational analysis of the mechanism.