The oxomanganese complex [H(2)O(terpy)Mn(III)(μ-O)(2)Mn(IV)(terpy)H(2)O](3+) (1, terpy = 2,2':6-2″-terpyridine) is a biomimetic model of the oxygen evolving complex of photosystem II with terminal water ligands. When bound to TiO(2) surfaces, 1 is activated by primary oxidants (e.g., Ce(4+)(aq), or oxone in acetate buffers) to catalyze the oxidation of water yielding O(2) evolution [G. Li et al...

We report the first high-frequency and -field electron paramagnetic resonance (HFEPR) study of a Mn(III) N-confused porphyrin (NCP) complex (NCP is also known as inverted porphyrin or 2-aza-21-carbaporphyrin). We have found a striking variation in the electronic properties of the S = 2 Mn(III) ion coordinated by NCP compared to other Mn(III) porphyrinoid complexes. Thus, inversion of a single p...

Arsenite (As(III)) oxidation by manganese oxides (Mn-oxides) serves to detoxify and, under many conditions, immobilize arsenic (As) by forming arsenate (As(V)). As(III) oxidation by Mn(IV)-oxides can be quite complex, involving many simultaneous forward reactions and subsequent back reactions. During As(III) oxidation by Mn-oxides, a reduction in oxidation rate is often observed, which is attri...

We have synthesized the first {Mn( iii )OH} complex in an all O-donor environment K 2 [Mn(OH)(pin F ) ], 3, formed by deprotonation of corresponding )OH } complex, K[Mn(OH )(pin 1. Complex 3 oxidizes substrates with weak N–H and O–H bonds.

The asymmetric unit of the title complex, {[Mn(C(20)H(10)Br(2)N(3)O(5))(H(2)O)]·(CH(3))(2)NCHO}(n), consists of one Mn(III) ion, one (E)-5-bromo-N-[2-(5-bromo-2-oxidobenzyl-idene-amino)-4-nitro-phen-yl]-2-oxidobenzamidate ligand (Schiff base), one water mol-ecule and an N,N-dimethyl-formamide mol-ecule. The coordination geometry around the Mn(III) ion is a distorted octa-hedron, being surrounde...

An unusual [Mn(IV)Gd(III)(2)(mu(3)-O(2-))](8+) triangular complex has been prepared from the initial use of 2,6-diacetylpyridine dioxime (dapdoH(2)) in 3d/4f cluster chemistry. The complex has an S = (13)/(2) ground state, with exchange parameters J = +0.49 cm(-1) and J' = -0.12 cm(-1) [H = -2J(S(i) x S(j)) convention] for the Gd(III)...Mn(IV) and Gd(III)...Gd(III) interactions, respectively. T...

The initial employment of alpha-benzoin oxime (bzoxH(2)) in higher oxidation state 3d metal cluster chemistry has provided access to a new enneanuclear Mn(III) complex with an unprecedented metal-core topology consisting of two triangular [Mn(3)(mu(3)-Omicron(2-))(mu-OmicronNu)(3)](4+) fragments connected by a linear [Mn(3)(mu-OmicronNu)(6)](3+) unit. The Mn(III)(9) cluster is antiferromagnetic...