Foster, J. Beauchamp
Aug 1, 1975
Citations
0
Influential Citations
62
Citations
Journal
Journal of the American Chemical Society
Abstract
The gas-phase ion chemistry of iron pentacarbonyl is characterized using the techniques of ion cyclotron resonance spectroscopy. The ion-molecule reactions of iron pentacarbonyl alone result in the formation of polynuclear clusters containing up to four iron atoms. In mixtures of iron pentacarbonyl with other species, substitution reactions are observed in which carbon monoxide is replaced by a wide variety of sigma- and ..pi..-bonding ligands. Many of these reactions result in the formation of unusual sigma- and ..pi..-bonded organometallic complexes. The basicity of Fe(CO)/sub 5/ in the gas phase is determined by examining proton transfer reactions in mixtures with species of known proton affinity. It is found that PA(Fe(CO)/sub 5/) = 204 +- 3 kcal/mole, making iron pentacarbonyl only slightly less basic than ammonia. Since the reported experiments are performed at low pressure in the gas phase, they provide information relating to the intrinsic reactivity of transition metal complexes in the absence of complicating solvation phenomena.