A Mononuclear Fe(III) Single Molecule Magnet with a 3/2↔5/2 Spin Crossover

The air stable complex [(PNP)FeCl(2)] (1) (PNP = N[2-P(CHMe(2))(2)-4-methylphenyl](2)(−)), prepared from one-electron oxidation of [(PNP)FeCl] with ClCPh(3), displays an unusual S = 3/2 to S = 5/2 transition above 80 K as inferred by the dc SQUID magnetic susceptibility measurement. The ac SQUID magnetization data, at zero field and between frequencies 10 and 1042 Hz, clearly reveals complex 1 to undergo a frequency dependent of the out-of-phase signal and thus be a single molecular magnet with a thermally activated barrier of U(eff) = 32-36 cm(−1) (47 - 52 K). Variable temperature Mössbauer data also corroborate a significant temperature dependence in δ and ΔE(Q) values for 1, which is in agreement with the system undergoing a change in spin state. Likewise, variable temperature X-band EPR spectra of 1 reveals the S = 3/2 to be likely the ground state with the S = 5/2 being close in energy. Multi-edge XAS absorption spectra suggest the electronic structure of 1 to be highly covalent with an effective iron oxidation state that is more reduced than the typical ferric complexes due to the significant interaction of the phosphine groups in PNP and Cl ligands with iron. A variable temperature single crystal X-ray diffraction study of 1 collected between 30-300 K also reveals elongation of the Fe–P bond lengths and increment in the Cl–Fe–Cl angle as the S = 5/2 state is populated. Theoretical studies show overall similar orbital pictures except for the d(z(2)) orbital which is the most sensitivity to change in the geometry and bonding where the quartet ((4)B) and the sextet ((6)A) states are close in energy

Sulfonamido-Pincer Complexes of Cu(II) and the Electrocatalysis of O₂ Reduction

Heteroleptic copper complexes of an asymmetrical pincer ligand containing a central anionic sulfonamide donor (pyridine-2-yl-sulfonyl)(quinolin-8-yl)-amide (psq), which contains a central anionic sulfonamido donor have been prepared. Meridional κ3-N,N″,N‴ binding with the co-ligands acetate, chloride, or acetonitrile (MeCN), trans to the central sulfonamido N-donor, is revealed by the X-ray crystal structures of [Cu(OAc)(psq)(H2O)], [CuCl(psq)]2, and [Cu(psq)(MeCN)](PF6). Either overall distorted square pyramidal or octahedral geometries of the copper atom are satisfied by coordinated water in the case of the acetate complex or interactions with periphery sulfonamido oxygen atoms on adjacent molecules in the dimeric chloride and 1D polymeric acetonitrile complexes. The cyclic voltammogram (CV) of [Cu(OAc)(psq)(H2O)] shows a quasi-reversible CuII/CuI reduction at −0.930 V (vs Fc+/Fc0, MeCN), and an irreversible CuII/CuI reduction for [Cu(psq)(MeCN)](PF6) is seen at −0.838 V. This signal is split into two quasi-reversible redox processes on the addition of 2,2,2-trifluoroethanol (TFE). This suggests that TFE pushes a solution equilibrium toward a dimeric acetate complex analogous to [CuCl(psq)]2, which shows two quasi-reversible waves at −0.666 V and −0.904 V vs Fc+/Fc0 consistent with its dimeric solid-state structure. A comparison of the CVs of [Cu(OAc)(psq)(H2O)] under either a N2 or an O2 atmosphere revealed that this complex catalyzes turnover electro-reduction of O2 to H2O2 and H2O. The rate of reaction increases on addition of a weak organic acid, and a coulombic efficiency of 48% for H2O2 was determined by iodometric titration. We propose that a CuI complex formed on electroreduction binds O2 to yield an intermediate superoxide complex. On electron and proton transfer to this species, a bifurcated route back to the O2-activating CuI complex is feasible with either release of H2O2 or O-O cleavage resulting in the liberation of H2O. The CuI complex is regenerated by subsequent reduction and protonation to close the cycle.</p