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The chains in complex [Mn(TPP)][Mn(TPP)(CN)2] (H2TPP = meso-tetra(4-phenyl)-porphyrin) demonstrate perfect linearity, and are well isolated with the nearest interchain Mn-Mn separation of 12.95 A. Ferromagnetic coupling is present among adjacent Mn(iii) ions, and single-chain magnet (SCM) behaviour is verified. The Royal Society of Chemistry.

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Copper(II) complexes of the ligands tris(2-pyridylmethyl)amine (tpyma), tris(2-pyridylethyl)amine (tpyea), tris(3,5-dimethylpyrazol-1-ylmethyl)amine (tpzma) and tris(3,5-dimethylpyrazol-1-ylethyl)amine (tpzea) were prepared.The complexes, Cl or 2, were characterized by a combination of absorption and EPR spectroscopies and chemical analysis.The ability of the complexes to oxidize 3,5-di-tert-butylcatechol to 3,5-di-tert-butyl-o-benzoquinone has been studied and the results show that the rate of reaction is dependent on the nature of the heterocyclic donor, its basicity, steric considerations, the chelate ring size and the type of exogenous donor present.Large variations in the rate were observed with the most effective catalysts being those with pyridine donors which formed six-membered chelate rings; the complex 2 was the most active while 2 and Cl were inactive.Electrochemical data for the series of compounds show that there is a non-linear relationship between their ability to oxidize catechols and their reduction potentials.The most effective catalysts were those complexes which exhibited reduction potentials close to 0.00 V, while those that deviated from that potential by 200-300 mV in either direction were largely inactive.Within the range of complexes which were active, a steric match between the substrate and the complex also largely defined their reactivity.Comparisons to the biological system tyrosinase are drawn.

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Artificial photosynthesis is envisioned as a promising strategy to convert sunlight, a practically unlimited and sustainable source of energy, into chemical fuels. In this scheme, the oxidation of water molecules is necessary to provide the electrons than will be employed in the synthesis of chemical fuels. Water oxidation is a particularly challenging reaction because it is a thermodynamically uphill multielectronic process with large activation barriers, but it is key for the realization of artificial photosynthesis because water is the only earth abundant molecule that can provide electrons in a massive and sustainable manner. Therefore, catalysts are needed for eluding the large intrinsic kinetic barriers of the reaction. In nature, water oxidation is catalyzed by a Mn tetrameric species, which enables O?O formation under the inherent mild physiological conditions trough a putative high valent manganese oxo species. Taking natural water oxidation as model, molecular catalysts operating under homogeneous conditions have been explored with the objective of providing basic understanding at molecular scale of the factors that govern this reaction, which eventually will receive utility in the design of efficient water oxidation devices. Traditionally, water oxidation has been studied with ruthenium and manganese based systems, but more recently attention has been shifted toward catalysts based on iridium and first row transition metals: the former due to their extraordinary performance and the latter because of their favorable cost, availability and environmental impact when compared with second and third row transition metals. The topic has been very actively explored and important lessons have been gained. Catalysts based on first row transition metals poise specific problems in terms of stability because generally their metal-ligand bonds are labile and because reaching their high oxidation states require high oxidation potentials. Consequently, high valent states of these metals are exceedingly reactive, readily prone to engage in oxidative decomposition paths. Catalyst design is crucial for circumventing these problems and has enabled the discovery of extraordinarily reactive yet reasonably stable catalysts, comparable to the best examples based on second and third row transition metals. The following chapter reviews key contributions to the field. The manuscript does not intend to be comprehensive, but instead, selected and in our opinion representative examples are discussed.

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A novel series of dinuclear squarato-bridged copper(II) and nickel(II) complexes [Cu2(TPA)2(mu1,3-C 4O4)](ClO4)2·4H2O (1), [Cu2(MeDPA)2(mu1,3-C4O 4)(H2O)4](ClO4)2 (2) and [Ni2(TPA)2(mu1,2-C4O 4)(H2O)2](ClO4)2 (3) [C4O42- = dianion of 3,4-dihydroxycyclobut-3- en-1,2-dione (squaric acid), MeDPA = N-methylbis(2-pyridylmethyl)amine, TPA = tris(2-pyridylmethyl)amine] were synthesized and structurally characterized by X-ray crystallography. The spectral and structural characterizations as well as their magnetic properties are reported. In this series, the structures consist of the ClO4- groups as counterions and the C 4O42- anions bridging the two MII centers in a mu-1,3- (1 and 2) or in a mu-1,2-bis(monodentate) (3) bonding fashion. The coordination geometry around the five-coordinate CuII centers in 1 is a distorted trigonal bipyramid, where the coordination environment is achieved by the four N-donor atoms of the TPA ligand and one oxygen atom of the bridging squarato ligand. The complexes 2 and 3 adopt a distorted octahedral geometry. The six-coordinate 4+2 envi-ronment in 2 is achieved by the three N-atoms of the MeDPA ligand, by an oxygen atom of a bridging squarato ligand and, at longest distances, by two oxygen atoms from coordinated water molecules. In the nickel complex 3, the geometry is attained by the four N-atoms of TPA and by two oxygen atoms supplied by a coordinated water molecule and by a bridging squarato ligand. The results manifested the effects of the blocking amine variations on the structure and on the bonding mode of the bridging squarato ligand. The complexes show antiferromagnetic coupling with |J| = 9.1 and 1.2 cm-1 in the mu-1,3-bridged squarato compounds 1 and 2, and with J = -1.4cm-1 in the corresponding mu-1,2-bridged squarato complex 3. The magnetic properties are discussed in relation to other related compounds and the structural data. Wiley-VCH Verlag GmbH & Co. KGaA, 2008.

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The reaction of the lanthanide salts LnI3(thf)4 and Ln(OTf)3 with tris(2-pyridylmethyl)amine (tpa) was studied in rigorously anhydrous conditions and in the presence of water. Under rigorously anhydrous conditions the successive formation of mono- and bis(tpa) complexes was observed on addition of 1 and 2 equiv of ligand, respectively. Addition of a third ligand equivalent did not yield additional complexes. The mono(tpa) complex [Ce(tpa)l3] (1) and the bis(tpa) complexes [Ln(tpa) 2]X3 (X = I, Ln = La(III) (2), Ln = Ce(III) (3), Ln = Nd(III) (4), Ln = Lu(III) (5); X = OTf, Ln = Eu(III) (6)) were isolated under rigorously anhydrous conditions and their solid-state and solution structures determined. In the presence of water, 1H NMR spectroscopy and ES-MS show that the successive addition of 1-3 equiv of tpa to triflate or iodide salts of the lanthanides results in the formation of mono(tpa) aqua complexes followed by formation of protonated tpa and hydroxo complexes. The solid-state structures of the complexes [Eu(tpa)(H2O)2(OTf) 3] (7), [Eu(tpa)(mu-OH)(OTf)2]2 (8), and [Ce(tpa)(mu-OH)(MeCN)(H2O]2I4 (9) have been determined. The reaction of the bis(tpa) lanthanide complexes with stoichiometric amounts of water yields a facile synthetic route to a family of discrete dimeric hydroxide-bridged lanthanide complexes prepared in a controlled manner. The suggested mechanism for this reaction involves the displacement of one tpa ligand by two water molecules to form the mono(tpa) complex, which subsequently reacts with the noncoordinated tpa to form the dimeric hydroxo species.

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A di-nuclear compound, [(CoTPA)2(1,4-BQ)][AsF6]3 (1) (TPA = tris(2-pyridylmethyl)amine, 1,4-BQ = deprotonated 2,5-dihydroxy-1,4-benzoquinone), was formed by one electron oxidation of [(CoTPA)2(1,4-BQ)]2+ cations. The compound was characterized by X-ray diffraction, electrochemistry, ESR, thermal- and photo-induced magnetic measurements. Variable temperature magnetic measurements have demonstrated that valence tautomeric transition with a small hysteresis around room temperature and photo-excited phenomenon is exhibited. In addition, temperature-dependent hs-ls relaxation of the converted high-spin fraction after irradiation was also studied.

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Homogeneous Fe and Mn oxidation catalysts can be immobilized on silica, zeolites, clays, layered double hydroxides and polymers. In addition to the well-known porphyrin catalysts, there is increasing interest in complexes with non-planar ligands. Based on a selection of examples, this paper discusses heterogenization methods, and the effects of heterogenization on the catalytic activity.

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TAML activators of peroxides are iron(III) complexes. The ligation by four deprotonated amide nitrogens in macrocyclic motifs is the signature of TAMLs where the macrocyclic structures vary considerably. TAML activators are exceptional functional replicas of the peroxidases and cytochrome P450 oxidizing enzymes. In water, they catalyze peroxide oxidation of a broad spectrum of compounds, many of which are micropollutants, compounds that produce undesired effects at low concentrations – as with the enzymes, peroxide is typically activated with near-quantitative efficiency. In nonaqueous solvents such as organic nitriles, the prototype TAML activator gave the structurally authenticated reactive iron(V)oxo units (FeVO), wherein the iron atom is two oxidation equivalents above the FeIII resting state. The iron(V) state can be achieved through the intermediacy of iron(IV) species, which are usually mu-oxo-bridged dimers (FeIVFeIV), and this allows for the reactivity of this potent reactive intermediate to be studied in stoichiometric processes. The present review is primarily focused at the mechanistic features of the oxidation by FeVO of hydrocarbons including cyclohexane. The main topic is preceded by a description of mechanisms of oxidation of thioanisoles by FeVO, because the associated studies provide valuable insight into the ability of FeVO to oxidize organic molecules. The review is opened by a summary of the interconversions between FeIII, FeIVFeIV, and FeVO species, since this information is crucial for interpreting the kinetic data. The highest reactivity in both reaction classes described belongs to FeVO. The resting state FeIII is unreactive oxidatively. Intermediate reactivity is typically found for FeIVFeIV therefore, kinetic features for these species in interchange and oxidation processes are also reviewed. Examples of using TAML activators for C-H bond cleavage applied to fine organic synthesis conclude the review.

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The cyclisation of N-allyl-N-substituted-alpha-polychloroamides is efficiently obtained through a copper-catalysed activators regenerated by electron transfer-atom transfer radical cyclisation process, with a metal load of only 0.5 mol%. The redox catalyst is introduced in its inactive form as copper(II) chloride/[nitrogen ligand] complex, and continuously regenerated to the active copper(I) chloride/[nitrogen ligand] species by ascorbic acid. To preserve the catalyst integrity, the hydrochloric acid, released after each regeneration cycle, has been quenched by carbonate. The choice of the solvent is critical, the best performance being observed in ethyl acetate-ethanol (3:1). Copyright

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Cyanide-bridged tri- and tetra-nuclear complexes, [Fe2IIIFeII(CN)6(tp*)2(tpa)] · 4MeCN · t-BuMeO (1) and [Fe4II(CN)4(bpy)4(bpym)4](PF6)4 · 6MeOH · 4H2O (2) (tp* = hydrotris(dimethylpyrazolyl)borate, bpym = 2,2?-bipyrimidine), were synthesized. Compound 1 has a right angled trinuclear core composed of two [Fe(CN)3(tp*)]- and one [Fe(tpa)]2+ units, while the tetra-nuclear complex in 2 has a square core composed of cyanide-bridged four Fe(II) ions. Magnetic susceptibility measurements revealed that both complexes showed thermally induced spin crossover.

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Metal catalyst and ligand design,
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