Iron carbonyl catalyzed rearrangement of BICYCLO[6.1.0]nonene systems

UNCG Author/Contributor (non-UNCG co-authors, if there are any, appear on document)
Luther Winfield Dasher (Creator)
The University of North Carolina at Greensboro (UNCG )
Web Site:
James Barborak

Abstract: Extensive use of a number of transition metals have been found to isomerize olefinic systems. Two major mechanisms have been proposed to explain olefin reorganization involving transition metal catalysts. One of these mechanisms is the metal hydride addition-elimination mechanism, and the other is the formation of a p-allyl metal hydride complex. Special attention is given to iron carbonyl catalysts and evidence is presented to support the p-allyl metal hydride mechanism, as well as evidence which appears to draw this particular mechanism into question. The p-allyl hydridoiron tricarbonyl mechanism, usually accepted as the correct mechanism, requires initial formation of a monoolefiniron tetracarbonyl complex. Upon loss of carbon monoxide from the complex, the coordinatively unsaturated iron tricarbonyl species extracts a hydrogen atom from the host molecule for stabilization to yield the p-allyl hydridoiron tricarbonyl complex. However, investigators were able to isolate the monoolefiniron tetracarbonyl complex by photochemical irradiation of 1,5-cyclooctadiene in the presence of Fe(CO)5, and showed that its thermal activity was contrary to that required by the p-allyl hydridoiron tricarbonyl mechanism. Heating the 1,5-cyclooctadieneiron tetracarbonyl complex produced the 1,5-cyclooctadiene bis(iron tetracarbonyl) complex, and unrearranged 1,5-cyclooctadiene, and no 1,3-cyclooctadiene or the corresponding complex was detected.

Additional Information

Language: English
Date: 1977
Ion catalysts
Transition metal catalysts

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