Linkage Isomerization Reactions of M(CO) 2 L Complexes (M = (η 5 -C 5 H 5 )Mn, (η 5 -C 5 H 5 )Re, or (η 6 -C 6 H 6 )Cr; L = 2,3-Dihydrofuran): A Step-Scan FTIR and DFT Study
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The linkage isomers, M(CO)2-(η1-(O)-2,3 DHF) and M(CO)2-(η2-(C,C)-2,3 DHF) [M = (η5- C5H5)Mn, (η5-C5H5)Re, (η6-C6H6)Cr; DHF = dihydrofuran] are formed upon photolysis of the parent M(CO)3 complexes in the presence of 2,3-DHF. The rearrangement of the oxygen bound to the thermodynamically favored π bound complex is followed on the millisecond to microsecond time scale using step-scan FTIR. The rate of the isomerization reaction increases in the order Re < Mn < Cr primarily due to a decrease in the activation enthalpy. The experimental data along with theoretical calculations suggest that the rearrangement proceeds intramolecularly in which the metal migrates from one functional group to another. © 2008 American Chemical Society.
author list (cited authors)
Bengali, A. A., Hall, M. B., & Wu, H.