Synthesis, characterization, and reactions of carbon dioxide bridged iron-rhenium complexes

Journal Article · Tue Nov 01 00:00:00 EST 1994 · Organometallics; (United States)

DOI:https://doi.org/10.1021/om00023a068· OSTI ID:6736343

Gibson, D H; Ye, M; Richardson, J F; Mashuta, M S ^[1]

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1. Univ. of Louisville, KY (United States)

A new [mu][sub 2]-[eta][sup 2]-CO[sub 2]-bridged complex, CpFe(CO)(PPh[sub 3])(CO[sub 2])Re(CO)[sub 4][P(OEt)[sub 3]], has been characterized. Thermolysis of 3 in benzene at 60[degree]C occurs with loss of CO from the rhenium center and provides a [mu][sub 2]-[eta][sup 3]-CO[sub 2]-bridged complex, 4a. Compound 4a has been characterized by X-ray crystallography. The structure shows that the rhenium atom has facial geometry and that the phosphorus ligands on iron and rhenium are anti; additionally, the plane of the CO[sub 2] ligand bisects the angle defined by the phosphorus, iron, and carbonyl carbon atoms. Exhaustive thermolysis of 3, in solution or in the solid state, leads to a different [mu][sub 2][eta][sup 3]-CO[sub 2]-bridged complex, 5b, in which the PPh[sub 3] and P(OEt)[sub 3] ligands have exchanged metal centers; 5b retains facial geometry at rhenium. Thermolysis pathways are proposed in which O-Re bond breaking in the [mu][sub 2]-[eta][sup 3] complexes is followed by ligand capture (CO or P(OEt)[sub 3]), facial to facial rearrangement, or phosphorus ligand exchange between the two metal centers. The thermolysis reactions clearly demonstrate the robust nature of the CO[sub 2] bridging ligands in this series of compounds. 14 refs., 4 figs., 3 tabs.

• OSTI ID: 6736343
• Journal Information: Organometallics; (United States), Vol. 13:11; ISSN 0276-7333
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
ORGANOMETALLIC COMPOUNDS
CHEMICAL REACTIONS
CRYSTAL STRUCTURE
MOLECULAR STRUCTURE
PYROLYSIS
SYNTHESIS
X-RAY SPECTRA
CHEMICAL REACTION KINETICS
CARBON DIOXIDE
IRON COMPLEXES
LIGANDS
RHENIUM COMPLEXES
CARBON COMPOUNDS
CARBON OXIDES
CHALCOGENIDES
COMPLEXES
DECOMPOSITION
KINETICS
ORGANIC COMPOUNDS
OXIDES
OXYGEN COMPOUNDS
REACTION KINETICS
SPECTRA
THERMOCHEMICAL PROCESSES
TRANSITION ELEMENT COMPLEXES
400201* - Chemical & Physicochemical Properties
400102 - Chemical & Spectral Procedures