Multireference Ground and Excited State Electronic Structures of Free- versus Iron Porphyrin-Carbenes

Iron porphyrin carbenes (IPCs) are important reaction intermediates in engineered carbene transferase enzymes and homogeneous catalysis. However, discrepancies between theory and experiment complicate the understanding of IPC electronic structure. In the literature, this has been framed as whether the ground state is an open-vs closed-shell singlet (OSS vs CSS). Here we investigate the structurally dependent ground and excited spin-state energetics of a free carbene and its IPC analogs with variable trans axial ligands. In particular, for IPCs, multireference ab initio wave function methods are more consistent with experiment and predict a mixed singlet ground state that is dominated by the CSS (Fe(II) <- {:C(X)Y}(0)) configuration (i.e., electrophilic carbene) but that also has a small, non-negligible contribution from an Fe(III)-{C(X)Y}(-center dot) configuration (hole in d(xz), i.e., radical carbene). In the multireference approach, the OSS-like excited states are metal-to-ligand charge transfer (MLCT) in nature and are energetically well above the CSS-dominated ground state. The first, lowest energy of these OSS-like excited states is predicted to be heavily weighted toward the Fe(III)-{C(X)Y}(-center dot) (hole in d(yz)) configuration. As expected from exchange considerations, this state falls energetically above a triplet of the same configuration. Furthermore, potential energy surfaces (PESs) along the IPC Fe-C(carbene) bond elongation exhibit increasingly strong mixings between CSS/OSS characters, with the Fe(III)-{C(X)Y}(-center dot) configuration (hole in d(xz)) growing in weight in the ground state during bond elongation. The relative degree of electrophilic/radical carbene character along this structurally relevant PES can potentially play a role in reactivity and selectivity patterns in catalysis. Future studies on IPC reaction coordinates should evaluate contributions from ground and excited state multireference character.