Electronic Structure and Spin Multiplicity of Iron Tetraphenylporphyrins in Their Reduced States as Determined by a Combination of Resonance Raman Spectroscopy and Quantum Chemistry.

Iron tetraphenylporphyrins are prime candidates as catalysts for CO reduction. Yet, even after 40 years of research, fundamental questions about the electronic structure of their reduced states remain, in particular as to whether the reducing equivalents are stored at the iron center or at the porphyrin ligand. In this contribution, we address this question by a combination of resonance Raman spectroscopy and quantum chemistry. Analysis of the data allows for an unequivocal identification of the porphyrin as the redox active moiety. Additionally, determination of the spin state of iron is possible by comparing the characteristic shifts of spin and oxidation-state-sensitive marker bands in the Raman spectrum with calculations of planar porphyrin model structures.