18 research outputs found
Theoretical study of the rheniumāalkane interaction in transition metalāalkane Ļ-complexes
Metalāalkane binding energies have been calculated for [CpRe(CO)(2)](alkane) and [(CO)(2)M(C(5)H(4))C [Image: see text] C(C(5)H(4))M(CO)(2)](alkane), where M = Re or Mn. Calculated binding energies were found to increase with the number of metalāalkane interaction sites. In all cases examined, the manganeseāalkane binding energies were predicted to be significantly lower than those for the analogous rheniumāalkane complexes. The metal (Mn or Re)āalkane interaction was predicted to be primarily one of charge transfer, both from the alkane to the metal complex (70ā80% of total charge transfer) and from the metal complex to the alkane (20ā30% of the total charge transfer)
Multiple-timescale photoreactivity of a model compound related to the active site of [fefe]-hydrogenase
Ultraviolet (UV) photolysis of (mu-S(CH2)(3)S)Fe-2(CO)(6) (1), a model compound of the Fe-hydrogenase enzyme system, has been carried out. When ultrafast UV-pump infrared (IR)-probe spectroscopy, steady-state Fourier transform IR spectroscopic methods, and density functional theory simulations are employed, it has been determined that irradiation of I in an alkane solution at 350 nm leads to the formation of two isomers of the 16-electron complex (mu-S(CH2)(3)S)Fe-2(CO)(5) within 50 ps with evidence of a weakly associated solvent adduct complex. 1 is subsequently recovered on timescales covering several minutes. These studies constitute the first attempt to study the photochemistry and reactivity of these enzyme active site models in solution following carbonyl ligand photolysis