Linkage Isomerization Reactions of M(CO)<sub>2</sub>L Complexes (M = (η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)Mn, (η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)Re, or (η<sup>6</sup>-C<sub>6</sub>H<sub>6</sub>)Cr; L = 2,3-Dihydrofuran): A Step-Scan FTIR and DFT Study
Ashfaq A. Bengali (1431769)Michael B. Hall (1341369)Hong Wu (105254)
Abstract
The linkage isomers, M(CO)<sub>2</sub>-(η<sup>1</sup>-(O)-2,3 DHF) and M(CO)<sub>2</sub>-(η<sup>2</sup>-(C,C)-2,3 DHF) [M = (η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>)Mn, (η<sup>5</sup>-C<sub>5</sub>H<sub><b>5</b></sub>)Re, (η<sup>6</sup>-C<sub>6</sub>H<sub>6</sub>)Cr; DHF = dihydrofuran] are formed upon photolysis of the parent M(CO)<sub>3</sub> 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.
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