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

Journal Article · Mon Oct 31 23:00:00 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), Journal Name: Organometallics; (United States) Vol. 13:11; ISSN ORGND7; ISSN 0276-7333
• Country of Publication: United States
• Language: English

Related Subjects

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