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The size of the organic cation dictates both the composition and the extended 3-D structure for hybrid organic/inorganic Prussian blue analogues (PBAs) of AaMnIIb(CN)a+2b (A = cation) stoichiometry. Alkali PBAs are typically cubic with both MC6 and M′N6 octahedral coordination sites and the alkali cation content depends on the M and M′ oxidation states. The reaction of MnII(O2CCH3)2 and A+CN– (A = NMe4, NEtMe3) forms a hydrated material of A3MnII5(CN)13 composition. A3MnII5(CN)13 forms a complex, 3-D extended structural motif with octahedral and rarely observed square pyramidal and trigonal bipyramidal MnII sites with a single layer motif of three pentagonal and one triangular fused rings. A complex pattern of MnIICN chains bridge the layers. (NMe4)3MnII5(CN)13 possesses one low-spin octahedral and four high-spin pentacoordinate MnII sites and orders as an antiferromagnet at 11 K due to the layers being bridged and antiferromagnetically coupled by the nonmagnetic cyanides. These are rare examples of intri...

The size of the organic cation dictates both the composition and the extended 3-D structure for hybrid organic/inorganic Prussian blue analogues (PBAs) of A

The synthesis of a pentadentate ligand with strategically designed fluorinated arene groups in the second coordination sphere of a nonheme iron center is reported. The oxidatively resistant fluorine substituents allow for the trapping and characterization of an Fe(IV)(O) complex at -20 °C. Upon warming of the Fe(IV)(O) complex, an unprecedented arene C-F hydroxylation reaction occurs. Computational studies support the finding that substrate orientation is a critical factor in the observed reactivity. This work not only gives rare direct evidence for the participation of an Fe(IV)(O) species in arene hydroxylation but also provides the first example of a high-valent iron-oxo complex that mediates aromatic C-F hydroxylation.

The new ligand N3Py(amide)SR and its Fe(II) complex [Fe(II)(N3Py(amide)SR)](BF4)2 (1) are described. Reaction of 1 with PhIO at -40 °C gives metastable [Fe(IV)(O)(N3Py(amide)SR)](2+) (2), containing a sulfide ligand and a single amide H-bond donor in proximity to the terminal oxo group. Direct evidence for H-bonding is seen in a structural analogue, [Fe(II)(Cl)(N3Py(amide)SR)](BF4)2 (3). Complex 2 exhibits rapid O-atom transfer (OAT) toward external sulfide substrates, but no intramolecular OAT. However, direct S-oxygenation does occur in the reaction of 1 with mCPBA, yielding sulfoxide-ligated [Fe(II)(N3Py(amide)S(O)R)](BF4)2 (4). Catalytic OAT with 1 was also observed.