Intramolecular CH Activation and Metallacycle Aromaticity in the Photochemistry of [FeFe]‐Hydrogenase Model Compounds in Low‐Temperature Frozen Matrices |
| |
| Authors: | Wyatt A. Thornley Prof. Thomas E. Bitterwolf |
| |
| Affiliation: | Department of Chemistry, University of Idaho, 875 Perimeter Dr., Moscow, ID 83844 (USA) |
| |
| Abstract: | The [FeFe]‐hydrogenase model complexes [(μ‐pdt){Fe(CO)3}2], [(μ‐edt){Fe(CO)3}2], and [(μ‐mdt){Fe(CO)3}2], where pdt=1,3‐propanedithiolate, edt=1,2‐ethanedithiolate, and mdt=methanedithiolate, undergo wavelength dependent photodecarbonylation in hydrocarbon matrices at 85 K resulting in multiple decarbonylation isomers. As previously reported in time‐resolved solution photolysis experiments, the major photoproduct is attributed to a basal carbonyl‐loss species. Apical carbonyl‐loss isomers are also generated and may undergo secondary photolysis, resulting in β‐hydride activation of the alkyldithiolate bridge, as well as formation of bridging carbonyl isomers. For [(μ‐bdt){Fe(CO)3}2], (bdt=1,2‐benzenedithiolate), apical photodecarbonylation results in generation of a 10 π‐electron aromatic FeS2C6H4 metallacycle that coordinates the remaining iron through an η5 mode. |
| |
| Keywords: | aromaticity C H activation hydrogenase matrix isolation photochemistry |
|
|
