NMR Reveals That a Highly Reactive Nonheme FeIV =O Complex Retains Its Six-Coordinate Geometry and S=1 State in Solution.

The [FeIV (O)(Me3 NTB)]2+ (Me3 NTB=tris[(1-methyl-benzimidazol-2-yl)methyl]amine) complex 1 has been shown by Mössbauer spectroscopy to have an S=1 ground state at 4 K, but is proposed to become an S=2 trigonal-bipyramidal species at higher temperatures based on a DFT model to rationalize its very high C-H bond-cleavage reactivity. In this work, 1 H NMR spectroscopy was used to determine that 1 does not have C3 -symmetry in solution and is not an S=2 species. Our results show that 1 is unique among nonheme FeIV =O complexes in retaining its S=1 spin state and high reactivity at 193 K, providing evidence that S=1 FeIV =O complexes can be as reactive as their S=2 counterparts. This result emphasizes the need to identify factors besides the ground spin state of the FeIV =O center to rationalize nonheme oxoiron(IV) reactivity.