Density Functional Calculations on Protonation of the [FeFe]-Hydrogenase Model Complex Fe2(-pdt)(CO)4(PMe3)2 and Subsequent Isomerization Pathways Academic Article uri icon

abstract

  • AbstractResults of density functional theory (DFT) calculations on the protonation of the [FeFe]hydrogenase model complex, Fe2(pdt)(CO)4(PMe3)2 (pdt = propane1,3dithiolate), show that diiron bridginghydride species are more stable than iron terminalhydride, sulfurhydride, or formyl isomers. Consistent with experimental observation, the transoid basal/basal forms are more stable than other H isomers. With an ether as the proton carrier, [Et2OH]+, the favoured reaction pathways appear to involve weak coordination to CO followed by transfer of the proton from ether to an iron terminal site rather than directly to the bridging site. These kinetically favoured terminalhydride species isomerize through a lowenergy RayDutt twist to produce the apical/basal bridginghydride isomer. This isomer rearranges over somewhat higher barrier Bailar twists to the cisoid and transoid basal/basal isomers, the former finally rearranging to the latter isomer.

published proceedings

  • EUROPEAN JOURNAL OF INORGANIC CHEMISTRY

author list (cited authors)

  • Liu, C., Peck, J., Wright, J. A., Pickett, C. J., & Hall, M. B.

citation count

  • 39

complete list of authors

  • Liu, Caiping||Peck, Jamie NT||Wright, Joseph A||Pickett, Christopher J||Hall, Michael B

publication date

  • March 2011

publisher