Gas-phase ion chemistry of iron pentacarbonyl by ion cyclotron resonance spectroscopy. New insights into the properties and reactions of transition metal complexes in the absence of complicating solvation phenomena

Journal Article · Wed Aug 20 00:00:00 EDT 1975 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00850a004· OSTI ID:7310399

Foster, M S; Beauchamp, J L

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.

• Research Organization: California Inst. of Tech., Pasadena
• OSTI ID: 7310399
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 97:17; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400104* -- Spectral Procedures-- (-1987)
400201 -- Chemical & Physicochemical Properties
400301 -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
ACETYLACETONE
ALKENES
AMMONIA
ANIONS
AROMATICS
BENZENE
BINDING ENERGY
CARBONYLS
CHALCOGENIDES
CHARGED PARTICLES
CHELATING AGENTS
CHEMICAL PROPERTIES
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CHLORINATED ALIPHATIC HYDROCARBONS
COMPLEXES
DEUTERIUM COMPOUNDS
ELECTRONEGATIVITY
ENERGY
ETHERS
ETHYLENE
FLUORINATED ALIPHATIC HYDROCARBONS
GAS ANALYSIS
HALOGENATED ALIPHATIC HYDROCARBONS
HYDRIDES
HYDROCARBONS
HYDROCHLORIC ACID
HYDROCYANIC ACID
HYDROGEN COMPOUNDS
INORGANIC ACIDS
ION CYCLOTRON RESONANCE SPECTROSCOPY
ION SPECTROSCOPY
IONS
IRON COMPLEXES
KETONES
KINETICS
METHYL ETHER
NITRIC OXIDE
NITROGEN COMPOUNDS
NITROGEN HYDRIDES
NITROGEN OXIDES
ORGANIC CHLORINE COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC FLUORINE COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
OXIDES
OXYGEN COMPOUNDS
REACTION KINETICS
REAGENTS
SPECTROSCOPY
TRANSITION ELEMENT COMPLEXES
WATER