Journal of the American Chemical Society, 06 March 2013, Vol.135
The mixed-valence diiron hydrido complex (μ-H)Fe2(pdt)(CO)2(dppv)2 ([H1](0), where pdt =1,3-propanedithiolate and dppv = cis-1,2-C2H2(PPh2)2), was generated by reduction of the differous hydride [H1](+) using decamethylcobaltocene. Crystallographic analysis shows that [H1](0) retains the stereochemistry of its precursor, where one dppv ligand spans two basal sites and the other spans apical and basal positions. The Fe---Fe bond elongates to 2.80 from 2.66 Å, but the Fe-P bonds only change subtly. Although the Fe-H distances are indistinguishable in the precursor, they differ by 0.2 Å in [H1](0). The X-band electron paramagnetic resonance (EPR) spectrum reveals the presence of two stereoisomers, the one characterized crystallographically and a contribution of about 10% from a second symmetrical (sym) isomer wherein both dppv ligands occupy apical-basal sites. The unsymmetrical (unsym) arrangement of the dppv ligands is reflected in the values of A((31)P), which range from 31 MHz for the basal phosphines to 284 MHz for the apical phosphine. Density functional theory calculations were employed to rationalize the electronic structure of [H1](0) and to facilitate spectral simulation and assignment of EPR parameters including (1)H and (31)P hyperfine couplings. The EPR spectra of [H1](0) and [D1](0) demonstrate that the singly occupied molecular orbital is primarily localized on the Fe center with the longer bond to H, that is, Fe(II)-H···Fe(I). The coupling to the hydride is A((1)H) = 55 and 74 MHz for unsym- amd sym-[H1](0), respectively. Treatment of [H1](0) with H(+) gives 0.5 equiv of H2 and [H1](+). Reduction of D(+) affords D2, leaving the hydride ligand intact. These experiments demonstrate that the bridging hydride ligand in this complex is a spectator in the hydrogen evolution reaction.
Catalysis (Homogeneous), Catalysis (Heterogeneous), Solar (Photovoltaic), Solar (Fuels), Photosynthesis (Natural and Artificial), Bio-Inspired, Hydrogen and Fuel Cells, Electrodes - Solar, Defects, Charge Transport, Spin Dynamics, Membrane, Materials and Chemistry By Design, Optics, Synthesis (Novel Materials), Synthesis (Self-Assembly)
View record in SciTech Connect