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Reactions of the unsymmetrical phenol ligand 2-(bis(2-pyridyimethyl)aminomethyl)-6-((2-pyridylmethyl)(benzyl)aminometh yl)-4-methylphenol with Mn(OAc)[sub 2]·4H[sub 2]O or Mn(H[sub 2]O)[sub 6](ClO[sub 4])[sub 2] in the presence of NaOBz affords the dimanganese(II) complexes 1(CH[sub 3]OH), [Mn[sub 2](L)(OAc)[sub 2](CH[sub 3]OH)](ClO[sub 4]), and 2(H[sub 2]O), [Mn[sub 2](L)(OBz)[sub 2](H[sub 2]O)](ClO[sub 4]), respectively. On the other hand, reaction of the ligand with hydrated manganese(III) acetate furnishes the mixedvalent derivative 3(H[sub 2]O), [Mn[sub 2](L)(OAc)[sub 2](H[sub 2]O)](ClO[sub 4])[sub 2]. The three complexes have been characterized by X-ray crystallography. 1(CH[sub 3]OH) crystallizes in the monoclinic system, space group P2[sub 1]/c, with a = 10.9215(6) Å, b = 20.2318(12) Å, c = 19.1354(12) Å, α = 90°, β = 97.5310(10)°, γ = 90°, V = 4191.7 A³, and Z = 4. 2(H[sub 2]O) crystallizes in the monoclinic system, space group P2[sub 1]/n, with a = 10.9215(6) Å, b = 20.2318(12) Å, c = 19.1354(12) Å, α = 90°, β = 97.5310(10)°, γ = 90°, V = 4191.7 ų, and Z = 4.3(H[sub 2]O) crystallizes in the monoclinic system, space group P2[sub 1]/c, with a = 11.144(6) Å, b = 18.737(10) Å, c = 23.949(13) Å, α = 90°, β = 95.910(10)°, γ = 90°, V-4974(5) ų, and Z = 4. Magnetic measurements revealed that the three compounds exhibit very similar magnetic exchange interactions -J = 4.3(3) cm[sup -1]. They were used to establish tentative magnetostructural correlations which show that for the dimanganese(II) complexes -J decreases when the Mn-O[sub phenoxo] distance increases as expected from orbital overlap considerations. For the dimanganese(II,III) complexes, crystallographic results show that the Mn[sup II]-O[sub phenoxo] and Mn[sup III]-O[sub phenoxo] bond lengths are inversely correlated. An... [ABSTRACT FROM AUTHOR]

Tris-copper centers are present at the active site of multicopper oxidases (MCO) which couple the four-electron reduction of molecular oxygen to water with the oxidation of substrates. Modelling these sites with small molecular complexes has thus attracted the interest of many groups in the (bio)inorganic community over the past three decades and still appears a challenge. These enzymes and their model complexes presently enjoy a renewed interest as potential non-precious metal catalyst for the Oxygen Reduction Reaction. Moreover recent work has revealed that tris-copper centers can catalyze methane oxidation. Therefore the elaboration of tris-copper system constitutes an important and timely issue. The aim of the present review is to analyze the various attempts at preparing tris-copper complexes in terms of strategy of ligand design. Of course the challenge to be met is to force three independent binding sites to converge and react in concert. Three main approaches have been developed to anchor these binding sites based on the use of (i) a node either (a) a single atom node (tren-based systems and related), or (b) an hexa -atom node (mesityl-based systems and derivatives), (ii) macrocyclic systems, and (iii) combination of mono- and dinuclear sites. The structures of the different systems will be described and analyzed accordingly. Then the various reactivities exhibited by these systems will be presented so as to evaluate how the ligand design influences the reactivity and to discern promising future directions. [ABSTRACT FROM AUTHOR]

The preparation and characterization of a series of complexes of the Yb and Eu cations in the oxidation state II and III with the tetradentate N,O-donor tripodal ligands (tris(2-pyridylmethyl)amine (TPA), BPA− (HBPA=bis(2-pyridylmethyl)(2-hydroxybenzyl)amine), BPPA− (HBPPA=bis(2-pyridylmethyl)(3.5-di- tert-butyl-2-hydroxybenzyl)amine), and MPA2− (H2MPA=(2-pyridylmethyl)bis(3.5-di- tert-butyl-2-hydroxybenzyl)amine) is reported. The X-ray crystal structures of the heteroleptic Ln2+ complexes [Ln(TPA)I2] (Ln=Eu, Yb) and [Yb(BPA)I(CH3CN)]2, of the Ln2+ homoleptic [Ln(TPA)2]I2 (Ln=Sm, Eu, Yb) and [Eu(BPA)2] complexes, and of the Ln3+ [Eu(BPPA)2]OTf and [Yb(MPA)2K(dme)2] (dme=dimethoxyethane) complexes have been determined. Cyclic voltammetry studies carried out on the bis-ligand complexes of Eu3+ and Yb3+ show that the metal center reduction occurs at significantly lower potentials for the BPA− ligand as compared with the TPA ligand. This suggests that the more electron-rich character of the BPA− ligand results in a higher reducing character of the lanthanide complexes of BPA− compared with those of TPA. The important differences in the stability and reactivity of the investigated complexes are probably due to the observed difference in redox potential. Preliminary reactivity studies show that whereas the bis-TPA complexes of Eu2+ and Yb2+ do not show any reactivity with heteroallenes, the [Eu(BPA)2] complex reduces CS2 to afford the first example of a lanthanide trithiocarbonate complex. [ABSTRACT FROM AUTHOR]

Reaction of the unsymmetrical phenol ligand 2-((bis(2-pyridylmethyl)amino)methyl)-6-(((2-pyridylmethyl)benzylamino)methyl)-4-methylphenol (HL-Bn) or its 2,6-dichlorobenzyl analogue (HL-BnCI2) with Fe(H2O)6(ClO4)2 in the presence of disodium m-phenylenedipropionate (Na2(mpdp)) followed by exposure to atmosphere affords the diiron(II,III) complexes [Fe2(L-Bn)(mpdp)(H2O)](ClO4)2 and [Fe2(L-BnCI2)(mpdp)(CH3OH)](CIO4)2, respectively. The latter complex has been characterized by X-ray crystallography. It crystallizes in the monoclinic system, space group P21/n, with a -13.3095(14) Å, b = 20.1073(19) Å, c = 19.4997(19) Å, α = 90°, β = 94.471(2)°, γ = 90°, V= 5202.6(9) ų, and Z = 4. The structure of the compound is very similar to that of [Fe2(L-Bn)(mpdp)(H2O)](BPh4)2 determined earlier, except for the replacement of a water by a methanol on the ferrous site. Magnetic measurements of [Fe2(LBn)(mpdp)(H2O)](BPh4)2 reveal that the two high-spin Fe ions are moderately antiferromagnetically coupled (J = -3.2(2) cm-1). Upon dissolution in acetonitrile the terminal ligand on the ferrous site is replaced by a solvent molecule. The acetonitrile-water exchange has been investigated by various spectroscopic techniques (UV-visible, NMR, Mössbauer) and electrochemistry. The substitution of acetonitrile by water is clearly evidenced by Mössbauer spectroscopy by a reduction of the quadrupole splitting value from 3.14 to 2.41 mm/s. In addition, it causes a 210 mV downshift of the oxidation potential of the ferrous site and a similar reduction of the stability domain of the mixed-valence state. Exhaustive electrolysis of a solution of [Fe2(L-Bn)(mpdp)(H2O)]2+ shows that the aqua diferric species is not stable and undergoes a chemical reaction which can be partly reversed by reduction to the mixedvalent state. This and other electrochemical observations suggest that upon oxidation of the diiron center to the diferric state the aqua ligand is deprotonated to a hydroxo. This hypothesis is supported by Mössbauer spectroscopy. Indeed, this species possesses a large quadrupole splitting value (ΔEQ ≥ 1.0 mm·s-1) similar to that of analogous complexes with a terminal phenolate ligand. This study illustrates the drastic effects of aqua ligand exchange and deprotonation on the electronic structure and redox potentials of diiron centers. [ABSTRACT FROM AUTHOR]

A new series of complexes of Eu2+ and Yb2+ with tripodal aminophenolate ligands are reported by M. Mazzanti and colleagues in their Full Paper on page 15188 ff. Cyclic voltammetry studies show that these ligands can be effectively used to tune the redox properties and reactivity of lanthanide ions possessing weak reducing power. The increased reducing power of Eu2+ in a homoleptic aminophenolate complex allows the reduction of CS2 and affords the first example of a lanthanide trithiocarbonate complex. [ABSTRACT FROM AUTHOR]