A Structural Model for the Iron-Nitrosyl Adduct of Gentisate Dioxygenase.

We present the synthesis, properties, and characterization of [Fe(T1Et4iPrIP)(NO)(H2O)2](OTf)2 (1) (T1Et4iPrIP = Tris(1-ethyl-4-isopropyl-imidazolyl)phosphine) as a model for the nitrosyl adduct of gentisate 1,2-dioxygenase (GDO). The further characterization of [Fe(T1Et4iPrIP)(THF)(NO)(OTf)](OTf) (2) which was previously communicated (Inorg. Chem. 2014, 53, 5414) is also presented. The weighted average Fe-N-O angle of 162° for 1 is very close to linear (≥ 165°) for these types of complexes. The coordinated water ligands participate in hydrogen bonding interactions. The spectral properties (EPR, UV-vis, FTIR) for 1 are compared with 2 and found to be quite comparable. Complex 1 closely follows the relationship between the Fe-N-O angle and NO vibrational frequency which was previously identified for 6-coordinate {FeNO}7 complexes. Liquid FTIR studies on 2 indicate that the ν(NO) vibration position is sensitive to solvent shifting to lower energy (relative to the solid) in donor solvent THF and shifting to higher energy in dichloromethane. The basis for this behavior is discussed. The K eq for NO binding in 2 was calculated in THF and found to be 470 M-1. Density functional theory (DFT) studies on 1 indicate donation of electron density to the iron center from the π* orbitals of formally NO-. Such a donation accounts for the near linearity of the Fe-N-O bond and the large ν(NO) value of 1791 cm-1.