Linkage Isomerization Reactions of M(CO)2L Complexes (M = (5-C5H5)Mn, (5-C5H5)Re, or (6-C6H6)Cr; L = 2,3-Dihydrofuran): A Step-Scan FTIR and DFT Study Academic Article uri icon

abstract

  • The linkage isomers, M(CO)2-(1-(O)-2,3 DHF) and M(CO)2-(2-(C,C)-2,3 DHF) [M = (5- C5H5)Mn, (5-C5H5)Re, (6-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 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.

published proceedings

  • Organometallics

author list (cited authors)

  • Bengali, A. A., Hall, M. B., & Wu, H.

publication date

  • January 1, 2008 11:11 AM