Mechanism of [gamma-H2SiV2W10O40](4-)-catalyzed epoxidation of alkenes with hydrogen peroxide

The mechanism of [gamma-H2SiV2W10O40]4--catalyzed epoxidation of alkenes with hydrogen peroxide in acetonitrile/tert-butyl alcohol was investigated. The negative Hammett rho+ (-0.88) for the competitive oxidation of p-substituted styrenes and the low XSO (XSO = (nucleophilic oxidation)/(total oxidation)) value of <0.01 for the [gamma-H2SiV2W10O40]4--catalyzed oxidation of thianthrene-5-oxide reveal that the strong electrophilic oxidant species is formed on [gamma-H2SiV2W10O40]4- (I). The preferable formation of trans-epoxide for the epoxidation of 3-substituted cyclohexenes shows the steric constraints of the active oxidant on I. The 51V NMR, 183W NMR, and CSI-MS spectroscopy show that the reaction of I with hydrogen peroxide leads to the reversible formation of a hydroperoxo species [gamma-HSiV2W10O39OOH]4- (II). The successive dehydration of II forms III, which possibly has an active oxygen species of a mu-eta2:eta2-peroxo group. The kinetic and spectroscopic studies show that the present epoxidation proceeds via III. The energy diagram of the epoxidation with density functional theory (DFT) supports the idea.     

Polyoxometalate catalysts: toward the development of green H2O2-based epoxidation systems

This paper describes the development of green, efficient H(2)O(2)-based epoxidation systems with three kinds of polyoxometalates: (i) a dinuclear peroxotungstate [W(2)O(3)(O(2))(4)(H(2)O)(2)](2-) (I), (ii) a divacant lacunary polyoxotungstate [gamma-SiW(10)O(34)(H(2)O)(2)]4 (II), (iii) and a divanadium-substituted polyoxotungstate [gamma-1,2-H(2)SiV(2)W(10)O(40)](4-) (III). The highly chemo-, regio-, and diastereoselective epoxidation of various allylic alcohols with only 1 equiv H(2)O(2) in water can be efficiently catalyzed by potassium salt of I (K-I). The catalyst K-I can be recycled with the retention of the catalytic performance. Protonation of a divacant lacunary polyoxotungstate [gamma-SiW(10)O(36)](8-) gives [gamma-SiW(10)O(34)(H(2)O)(2)](4-) (II) with two aquo ligands. The tetra-n-butylammonium salt of II (TBA-II) catalyzes epoxidation of common olefins including propylene with >or=99% selectivity to epoxide and >or=99% efficiency of H(2)O(2) utilization. The bis(mu-hydroxo)bridged dioxovanadium site in [gamma-1,2-H(2)SiV(2)W(10)O(40)](4-) (III) can also efficiently catalyze epoxidation of a variety of olefins with 1 equiv H(2)O(2). Notably, the system with III shows unique stereospecificity, diastereoselectivity, and regioselectivity for the epoxidation of cis/trans olefins, 3-substituted cyclohexenes, and nonconjugated dienes, respectively, which are quite different from those reported for epoxidation systems up to now. Furthermore, the heterogenization of the mentioned polyoxometalates can be achieved by using ionic liquid-modified SiO(2) as a support without loss of catalytic performance.     

Transition metal containing decatungstosilicate dimer [M(H(2)O)(2)(gamma-SiW(10)O(35))(2)](10-) (M = Mn(2+), Co(2+), Ni(2+))

The new, monometal substituted silicotungstates [Mn(H(2)O)(2)(gamma-SiW(10)O(35))(2)](10-) (1), [Co(H(2)O)(2)(gamma-SiW(10)O(35))(2)](10-) (2) and [Ni(H(2)O)(2)(gamma-SiW(10)O(35))(2)](10-) (3) have been synthesized and isolated as the potassium salts K(10)[Mn(H(2)O)(2)(gamma-SiW(10)O(35))(2)] x 8.25 H(2)O (K-1), K(10)[Co(H(2)O0(2)(gamma-SiW(10)O(35))(2)] x 8.25 H(2)O (K-2) and K(10)[Ni(H(2)O)(2)(gamma-SiW(10)O(35))(2)] x 13.5 H(2)O (K-3), which have been characterized by IR spectroscopy, single crystal X-ray diffraction, elemental analysis and cyclic voltammetry. Polyanions 1-3 are composed of two (gamma-SiW(10)O(36)) units fused on one side via two W-O-W' bridges and on the other side by an octahedrally coordinated trans-MO(4)(OH(2))(2) transition metal fragment, resulting in a structure with C(2v) point group symmetry. Anions 1-3 were synthesized by reaction of the dilacunary precursor [gamma-SiW(10)O(36)](8-) with Mn(2+), Co(2+) and Ni(2+) ions, respectively, in 1 M KCl solution at pH 4.5. The electrochemical properties of 1-3 were studied by cyclic voltammetry and controlled potential coulometry in a pH 5 buffer medium. The waves associated with the W-centers are compared with each other and with those of the parent lacunary precursor [gamma-SiW(10)O(36)](8-) in the same medium. They appear to be dominated by the acid-base properties of the intermediate reduced species. A facile merging of the waves for 3 is observed while those for 1 and 2 remain split. Controlled potential coulometry of the single wave of 3 or the combined waves of 1 and 2 is accompanied by catalysis of the hydrogen evolution reaction. No redox activity was detected for the Ni(2+) center in 3, whereas the Co(2+) center in 2 shows a one-electron redox process. The two-electron, chemically reversible process of the Mn(2+) center in 1 is accompanied by a film deposition on the electrode surface.     

Kinetics and mechanism of the [Ru(III)(edta)(H2O)](-)-mediated oxidation of cysteine by H2O2

The kinetics and mechanism of the [Ru(III)(edta)(H(2)O)](-)-mediated oxidation of cysteine (RSH) by hydrogen peroxide (edta(4-) = ethylenediaminetetraacetate), were studied in detail as a function of both the hydrogen peroxide and cysteine concentrations at pH 5.1 and room temperature. The kinetic traces reveal clear evidence for a catalytic process in which hydrogen peroxide reacts directly with cysteine coordinated to the Ru(III)(edta) complex in the form of [Ru(III)(edta)SR](2-). A parallel process in which [Ru(III)(edta)(H(2)O)](-) first reacts with H(2)O(2) to produce [Ru(V)(edta)O](-) and subsequently oxidizes cysteine, is orders of magnitude slower than the [Ru(III)(edta)(H(2)O)](-)-mediated oxidation in which cysteine rapidly coordinates to [Ru(III)(edta)(H(2)O)](-) prior to the reaction with H(2)O(2). HPLC product analyses revealed the formation of cystine (RSSR) as major product along with cysteine sulfinic acid (RSO(2)H) in the reaction system, and established the catalytic role of [Ru(III)(edta)(H(2)O)](-). Simulations were performed to account for the rather complex kinetic traces in terms of the suggested reaction mechanism. The results of the simulations support the proposed reaction mechanism that involves the oxidation of coordinated cysteine to cysteine sulfenic acid (RSOH), which subsequently rapidly reacts with H(2)O(2) and RSH to form RSO(2)H and RSSR, respectively.     

Syntheses and crystal structures of two new bismuth hydroxyl borates containing [Bi2O2]2+ layers: Bi2O2[B3O5(OH)] and Bi2O2[BO2(OH)

Two new bismuth hydroxyl borates, Bi(2)O(2)[B(3)O(5)(OH)] (I) and Bi(2)O(2)[BO(2)(OH)] (II), have been synthesized under hydrothermal conditions. Their structures were determined by single-crystal and powder X-ray diffraction data, respectively. Compound I crystallizes in the orthorhombic space group Pbca with the lattice constants of a = 6.0268(3) ?, b = 11.3635(6) ?, and c = 19.348(1) ?. Compound II crystallizes in the monoclinic space group Cm with the lattice constants of a = 5.4676(6) ?, b = 14.6643(5) ?, c = 3.9058(1) ?, and β = 135.587(6)°. The borate fundamental building block (FBB) in I is a three-ring unit [B(3)O(6)(OH)](4-), which connects one by one via sharing corners, forming an infinite zigzag chain along the a direction. The borate chains are further linked by hydrogen bonds, showing as a borate layer within the ab plane. The FBB in II is an isolated [BO(2)(OH)](2-) triangle, which links to two neighboring FBBs by strong hydrogen bonds, resulting in a borate chain along the a direction. Both compounds contain [Bi(2)O(2)](2+) layers, and the [Bi(2)O(2)](2+) layers combine with the corresponding borate layers alternatively, forming the whole structures. These two new bismuth borates are the first ones containing [Bi(2)O(2)](2+) layers in borates. The appearance of Bi(2)O(2)[BO(2)(OH)] (II) completes the series of compounds Bi(2)O(2)[BO(2)(OH)], Bi(2)O(2)CO(3), and Bi(2)O(2)[NO(3)(OH)] and the formation of Bi(2)O(2)[B(3)O(5)(OH)] provides another example in demonstrating the polymerization tendency of borate groups.     

New insights into the mechanism of oxodiperoxomolybdenum catalysed olefin epoxidation and the crystal structures of several oxo-peroxo molybdenum complexes

[Mo(O)(O(2))(2)(L)(2)] compounds (L = pz, pyrazole; dmpz, 3,5-dimethylpyrazole) were reacted stoichiometrically, in the absence of an oxidant, with cis-cyclooctene in an ionic liquid medium where selective formation of the corresponding epoxide was observed. However, this oxo-transfer reaction was not observed for some other olefins, suggesting that alternative reaction pathways exist for these epoxidation processes. Subsequently, DFT studies investigating the oxodiperoxomolybdenum catalysed epoxidation model reaction for ethylene with hydrogen peroxide oxidant were performed. The well known Sharpless mechanism was first analysed for the [Mo(O)(O(2))(2)(dmpz)(2)] model catalyst and a low energy reaction pathway was found, which fits well with the observed experimental results for cis-cyclooctene. The structural parameters of the computed dioxoperoxo intermediate [Mo(O)(2)(O(2))(dmpz)(2)] in the Sharpless mechanism compare well with those found for the same moiety within the [Mo(4)O(16)(dmpz)(6)] complex, for which the full X-ray report is presented here. A second mechanism for the model epoxidation reaction was theoretically investigated in order to clarify why some olefins, which do not react stoichiometrically in the absence of an oxidant, showed low level conversions in catalytic conditions. A Thiel-type mechanism, in which the oxidant activation occurs prior to the oxo-transfer step, was considered. The olefin attack of the hydroperoxide ligand formed upon activation of hydrogen peroxide with the [Mo(O)(O(2))(2)(dmpz)(2)] model catalyst was not possible to model. The presence of two dmpz ligands coordinated to the molybdenum centre prevented the olefin attack for steric reasons. However, a low energy reaction pathway was identified for the [Mo(O)(O(2))(2)(dmpz)] catalyst, which can be formed from [Mo(O)(2)(O(2))(dmpz)(2)] by ligand dissociation. Both mechanisms, Sharpless- and Thiel-type, were found to display comparable energy barriers and both are accessible alternative pathways in the oxodiperoxomolybdenum catalysed olefin epoxidation. Additionally, the molecular structures of [Mo(O)(O(2))(2)(H(2)O)(pz)] and [Hdmpz](4)[Mo(8)O(22)(O(2))(4)(dmpz)(2)]·2H(2)O and the full X-ray report of [Mo(O)(O(2))(2)(pz)(2)] are also presented.     

Polyfluorinated quaternary ammonium salts of polyoxometalate anions: fluorous biphasic oxidation catalysis with and without fluorous solvents

[reaction: see text] Polyfluorinated quaternary ammonium cations, [CF(3)(CF(2))(7)(CH(2))(3)](3)CH(3)N(+) (R(F)N(+)), were synthesized and used as countercations for the [WZnM(2)(H(2)O)(2)(ZnW(9)O(34))(2)](12)(-) (M = Mn(II), Zn(II)) polyoxometalate. The (R(F)N(+))(12)[WZnM(2)(H(2)O)(2)(ZnW(9)O(34))(2)] compounds were fluorous biphasic catalysts for alcohol and alkenol oxidation, and alkene epoxidation with aqueous hydrogen peroxide. Reaction protocols with or without a fluorous solvent were tested. The catalytic activity and selectivity was affected by both the hydrophobicity of the solvent and the substrate.     

Structural and dynamical aspects of alkylammonium salts of a silicodecatungstate as heterogeneous epoxidation catalysts

The structural and dynamical aspects of alkylammonium salts of a silicodecatungstate [(CH(3))(4)N](4)[γ-SiW(10)O(34)(H(2)O)(2)] [C1], [(n-C(3)H(7))(4)N](4)[γ-SiW(10)O(34)(H(2)O)(2)] [C3], [(n-C(4)H(9))(4)N](4)[γ-SiW(10)O(34)(H(2)O)(2)] [C4], and [(n-C(5)H(11))(4)N](4)[γ-SiW(10)O(34)(H(2)O)(2)] [C5] were investigated. The results of sorption isotherms, XRD analyses, and solid-state NMR spectroscopy show that facile sorption of solvent molecules, flexibility of structures, and high mobility of alkylammonium cations are crucial to the uniform distribution of reactant and oxidant molecules throughout the bulk solid, which are related to the high catalytic activities for epoxidation of alkenes.     

Resonance raman investigation of equatorial ligand donor effects on the Cu(2)O(2)(2+) core in end-on and side-on mu-peroxo-dicopper(II) and bis-mu-oxo-dicopper(III) complexes

The effect of endogenous donor strength on Cu(2)O(2) bonds was studied by electronically perturbing [[(R-TMPA)Cu(II)]](2)(O(2))](2+) and [[(R-MePY2)Cu](2)(O(2))](2+) (R = H, MeO, Me(2)N), which form the end-on mu-1,2 bound peroxide and an equilibrium mixture of side-on peroxo-dicopper(II) and bis-mu-oxo-dicopper(III) isomers, respectively. For [[(R-TMPA)Cu(II)](2)(O(2))](2+), nu(O-O) shifts from 827 to 822 to 812 cm(-1) and nu(Cu)(-)(O(sym)) shifts from 561 to 557 to 551 cm(-1), respectively, as R- varies from H to MeO to Me(2)N. Thus, increasing the N-donor strength to the copper decreases peroxide pi(sigma) donation to the copper, weakening the Cu-O and O-O bonds. A decrease in nu(Cu-O) of the bis-mu-oxo-dicopper(III) complex was also observed with increasing N-donor strength for the R-MePY2 ligand system. However, no change was observed for nu(O-O) of the side-on peroxo. This is attributed to a reduced charge donation from the peroxide pi(sigma) orbital with increased N-donor strength, which increases the negative charge on the peroxide and adversely affects the back-bonding from the Cu to the peroxide sigma orbital. However, an increase in the bis-mu-oxo-dicopper(III) isomer relative to side-on peroxo-dicopper(II) species is observed for R-MePY2 with R = H < MeO < Me(2)N. This effect is attributed to the thermodynamic stabilization of the bis-mu-oxo-dicopper(III) isomer relative to the side-on peroxo-dicopper(II) isomer by strong donor ligands. Thus, the side-on peroxo-dicopper(II)/bis-mu-oxo-dicopper(III) equilibrium can be controlled by electronic as well as steric effects.     

Synthesis and magnetic properties of 3-D [Ru(II/III)(2)(O(2)CMe)(4)](3)[M(III)(CN)(6)] (M = Cr,Fe, Co)

Three-dimensional network structures of [Ru(II/III)(2)(O(2)CMe)(4)](3)[M(III)(CN)(6)] (M = Cr, Fe, Co) composition have been formed and their magnetic properties characterized. [Ru(II/III)(2)(O(2)CMe)(4)](3)[M(III)(CN)(6)] (M = Cr, Fe, Co) have nu(CN) IR absorptions at 2138, 2116, and 2125 cm(-1) and have body-centered unit cells (a = 13.34, 13.30, and 13.10 A, respectively) with -M-Ctbd1;N-Ru=Ru-Ntbd1;C-M- linkages along all three Cartesian axes. [Ru(II/III)(2)(O(2)CMe)(4)](3)[Cr(III)(CN)(6)] magnetically orders as a ferrimagnet (T(c) = 33 K) and has an unusual constricted hysteresis loop.     

Synthesis, characterization, and chiral behavior of S-bridged Co(III)Pt(II)Co(III) trinuclear complexes composed of bis(thiolato)-type octahedral units cis(S)-[Co(aet)(2)(en)](+) and/or trans(N)-[Co(D-pen- N,O,S)(2)](-) (aet = 2-aminoethanethiolate, D-pen = D-penicillaminate)

A series of linear-type Co(III)Pt(II)Co(III) trinuclear complexes composed of C(2)-cis(S)-[Co(aet)(2)(en)](+) (aet = 2-aminoethanethiolate) and/or Lambda(D)-trans(N)-[Co(D-pen-N,O,S)(2)](-) (D-pen = D-penicillaminate) were newly prepared, and their chiral behavior, which is markedly different from that of the corresponding Co(III)Pd(II)Co(III) complexes, is reported. The 1:1 reaction of an S-bridged Co(III)Ni(II)Co(III) trinuclear complex, [Ni[Co(aet)(2)(en)](2)]Cl(4), with K(2)[PtCl(4)] in water gave an S-bridged Co(III)Pt(II)Co(III) trinuclear complex, [Pt[Co(aet)(2)(en)](2)]Cl(4) ([1]Cl(4)), while the corresponding 1:2 reaction produced an S-bridged Co(III)Pt(II) dinuclear complex, [PtCl(2)[Co(aet)(2)(en)]]Cl ([2]Cl). Complex [1](4+) formed both racemic (DeltaDelta/LambdaLambda) and meso (DeltaLambda) forms, which were separated and optically resolved by cation-exchange column chromatography. An optically active S-bridged Co(III)Pt(II)Co(III) trinuclear complex having the pseudo LambdaLambda configuration, Lambda(D)Lambda(D)-[Pt[Co(D-pen-N,O,S)(2)](2)](0) (Lambda(D)Lambda(D)-[3]), was also prepared by reacting Lambda(D)-trans(N)-K[Co(D-pen-N,O,S)(2)] with K(2)[PtCl(4)] in a ratio of 2:1 in water. Treatment of the racemic Delta/Lambda-[2]Cl with Lambda(D)-trans(N)-K[Co(D-pen-N,O,S)(2)] in a ratio of 1:1 in water led to the formation of LambdaLambda(D)- and DeltaLambda(D)-[Pt[Co(aet)(2)(en)][Co(D-pen-N,O,S)(2)]](2+) (LambdaLambda(D)- and DeltaLambda(D)-[4](2+)) and DeltaDelta(D)-[Pt[Co(aet)(2)(en)][Co(D-pen-N,S)(2)(H(2)O)(2)]](2+) (DeltaDelta(D)-[4'](2+)), besides trace amounts of Lambda(D)Lambda(D)-[3] and DeltaDelta- and DeltaLambda-[1](4+). These Co(III)Pt(II)Co(III) complexes were characterized on the basis of electronic absorption, CD, and NMR spectra, along with single-crystal X-ray analyses for DeltaDelta/LambdaLambda-[1]Cl(4), DeltaLambda-[1]Cl(4), and DeltaLambda(D)-[4]Cl(2). Crystal data: DeltaDelta/LambdaLambda-[1]Cl(4).6H(2)O, monoclinic, space group C2/c with a = 14.983(3) A, b = 19.857(4) A, c = 12.949(3) A, beta = 113.51(2) degrees, V = 3532(1) A(3), Z = 4; DeltaLambda-[1]Cl(4).3H(2)O, orthorhombic, space group Pbca with a = 14.872(3) A, b = 14.533(3) A, c = 14.347(2) A, V = 3100(1) A(3), Z = 4; DeltaLambda(D)-[4]Cl(2).6H(2)O, monoclinic, space group P2(1) with a = 7.3836(2) A, b = 20.214(1) A, c = 10.622(2) A, beta = 91.45(1) degrees V = 1682.0(4) A(3), Z = 2.     

Synthesis and catalysis of di- and tetranuclear metal sandwich-type silicotungstates [(gamma-SiW10O36)2M2(mu-OH)2]10- and [(gamma-SiW10O36)2M4(mu4-O)(mu-OH)6]8- (M = Zr or Hf)

The di- and tetranuclear metal sandwich-type silicotungstates of Cs10[(gamma-SiW10O36)2{Zr(H2O)}2(mu-OH)2] x 18 H2O (Zr2, monoclinic, C2/c (No. 15), a = 25.3315(8) A, b = 22.6699(7) A, c = 18.5533(6) A, beta = 123.9000(12) degrees, V = 8843.3(5) A(3), Z = 4), Cs10[(gamma-SiW10O36)2{Hf(H2O)}2(mu-OH)2] x 17 H2O (Hf2, monoclinic, space group C2/c (No. 15), a = 25.3847(16) A, b = 22.6121(14) A, c = 18.8703(11) A, beta = 124.046(3) degrees, V = 8974.9(9) A(3), Z = 4), Cs8[(gamma-SiW10O36)2{Zr(H2O)}4(mu4-O)(mu-OH)6] x 26 H2O (Zr4, tetragonal, P4(1)2(1)2 (No. 92), a = 12.67370(10) A, c = 61.6213(8) A, V = 9897.78(17) A(3), Z = 4), and Cs8[(gamma-SiW10O36)2{Hf(H2O)}4(mu4-O)(mu-OH)6] x 23 H2O (Hf4, tetragonal, P4(1)2(1)2 (No. 92), a = 12.68130(10) A, c = 61.5483(9) A, V = 9897.91(18) A(3), Z = 4) were obtained as single crystals suitable for X-ray crystallographic analyses by the reaction of a dilacunary gamma-Keggin silicotungstate K8[gamma-SiW10O36] with ZrOCl2 x 8 H2O or HfOCl2 x 8 H2O. These dimeric polyoxometalates consisted of two [gamma-SiW10O36](8-) units sandwiching metal-oxygen clusters such as [M2(mu-OH)2](6+) and [M4(mu4-O)(mu-OH)6](8+) (M = Zr or Hf). The dinuclear zirconium and hafnium complexes Zr2 and Hf2 were isostructural. The equatorially placed two metal atoms in Zr2 and Hf2 were linked by two mu-OH ligands and each metal was bound to four oxygen atoms of two [gamma-SiW10O36](8-) units. The tertanuclear zirconium and hafnium complexes Zr4 and Hf4 were isostructural and consisted of the adamantanoid cages with a tetracoordinated oxygen atom in the middle, [M4(mu4-O)(mu-OH)6](8+) (M = Zr or Hf). Each metal atom in Zr4 and Hf4 was linked by three mu-OH ligands and bound to two oxygen atoms of the [gamma-SiW10O36](8-) unit. The tetra-nuclear zirconium and hafnium complexes showed catalytic activity for the intramolecular cyclization of (+)-citronellal to isopulegols without formation of byproducts resulting from etherification and dehydration. A lacunary silicotungstate [gamma-SiW10O34(H2O)2](4-) was inactive, and the isomer ratio of isopulegols in the presence of MOCl2 x 8 H2O (M = Zr or Hf) were much different from that in the presence of tetranuclear complexes, suggesting that the [M4(mu4-O)(mu-OH)6](8+) core incorporated into the POM frameworks acts as an active site for the present cyclization. On the other hand, the reaction hardly proceeded in the presence of dinuclear zirconium and hafnium complexes under the same conditions. The much less activity is possibly explained by the steric repulsion from the POM frameworks in the dinuclear complexes.     

Metal coordination and in situ S-C bond cleavage of the bis(2-pyridylthio)methane ligand

The compound [2bpytmH](2)[I(3)](2)[I(2)], which contains protonated 2bpytm, and four neutral monomeric complexes [CoCl(2)(2bpytm)]·H(2)O (1), [CoBr(2)(2bpytm)] (2), [CoI(2)(2bpytm)]·1/2H(2)O (3) and [NiBr(2)(2bpytm)]·H(2)O (4) have been obtained during a study into the reactivity of the bis(2-pyridylthio)methane (2bpytm) ligand towards cobalt(II) and nickel(II) halides. Furthermore, a cyclic dimer [CuBr(2)(2bpytm)](2) (5) and a 1D polymer [CuBr(2)(2bpytm)](n)·CH(3)CN (6) have been obtained from copper(II)/(I) bromide salts. An unprecedented S-CH(2)-S activation and cleavage in 2bpytm has been observed on using copper(II) salts with organic and voluminous inorganic anions. The cleavage of 2bpytm enabled the isolation of copper(II) complexes containing the in situ generated ligands 2-pyridinethiolate, 2-pyridinesulfenate or 2-pyridinesulfonate.     

3d-Metal derivatives of the [Cu(I)(SO3)4]7- ion: structure and magnetism

The Cu(SO(3))(4)(7-) anion, which consists of a tetrahedrally coordinated Cu(I) centre coordinated to four sulfur atoms, is able to act as a multidentate ligand in discrete and infinite supramolecular species. The slow oxidation of an aqueous solution of Na(7)Cu(SO(3))(4) yields a mixed oxidation state, 2D network of composition Na(5){[Cu(II)(H(2)O)][Cu(I)(SO(3))(4)]}·6H(2)O. The addition of Cu(II) and 2,2'-bipyridine to an aqueous Na(7)Cu(SO(3))(4) solution leads to the formation of a pentanuclear complex of composition {[Cu(II)(H(2)O)(bipy)](4)[Cu(I)(SO(3))(4)]}(+); a combination of hydrogen bonding and π-π stacking interactions leads to the generation of infinite parallel channels that are occupied by disordered nitrate anions and water molecules. A pair of Cu(SO(3))(4)(7-) anions each act as a tridentate ligand towards a single Mn(II) centre when Mn(II) ions are combined with an excess of Cu(SO(3))(4)(7-). An anionic pentanuclear complex of composition {[Cu(I)(SO(3))(4)](2)[Fe(III)(H(2)O)](3)(O)} is formed when Fe(II) is added to a Cu(+)/SO(3)(2-) solution. Hydrated ferrous [Fe(H(2)O)(6)(2+)] and sodium ions act as counterions for the complexes and are responsible for the formation of an extensive hydrogen bond network within the crystal. Magnetic susceptibility studies over the temperature range 2-300 K show that weak ferromagnetic coupling occurs within the Cu(II) containing chains of Na(5){[Cu(II)(H(2)O)][Cu(I)(SO(3))(4)]}·6H(2)O, while zero coupling exists in the pentanuclear cluster {[Cu(II)(H(2)O)(bipy)](4)[Cu(I)(SO(3))(4)]}(NO(3))·H(2)O. Weak Mn(II)-O-S-O-Mn(II) antiferromagnetic coupling occurs in Na(H(2)O)(6){[Cu(I)(SO(3))(4)][Mn(II)(H(2)O)(2)](3)}, the latter formed when Mn was in excess during synthesis. The compound, Na(3)(H(2)O)(6)[Fe(II)(H(2)O)(6)](2){[Cu(I)(SO(3))(4)](2)[Fe(III)(H(2)O)](3)(O)}·H(2)O, contained trace magnetic impurities that affected the expected magnetic behaviour.     

Olefin epoxidation by alkyl hydroperoxide with a novel cross-bridged cyclam manganese complex: demonstration of oxygenation by two distinct reactive intermediates

Olefin epoxidation provides an operative protocol to investigate the oxygen transfer process in nature. A novel manganese complex with a cross-bridged cyclam ligand, MnIV(Me2EBC)(OH)2(2+) (Me2EBC = 4,11-dimethyl-1,4,8,11-tetraazabicyclo[6.6.2]hexadecane), was used to study the epoxidation mechanism with biologically important oxidants, alkyl hydroperoxides. Results from direct reaction of the freshly synthesized manganese(IV) complex, [Mn(Me2EBC)(OH)2](PF6)2, with various olefins in neutral or basic solution, and from catalytic epoxidation with oxygen-labeled solvent, H2 18O, eliminate the manganese oxo moiety, Mn(IV)=O, as the reactive intermediate and obviate an oxygen rebound mechanism. Epoxidations of norbornylene under different conditions indicate multiple mechanisms for epoxidation, and cis-stilbene epoxidation under atmospheric 18O2 reveals a product distribution indicating at least two distinctive intermediates serving as the reactive species for epoxidation. In addition to alkyl peroxide radicals as dominant intermediates, an alkyl hydroperoxide adduct of high oxidation state manganese(IV) is suggested as the third kind of active intermediate responsible for epoxidation. This third intermediate functions by the Lewis acid pathway, a process best known for hydrogen peroxide adducts. Furthermore, the tert-butyl peroxide adduct of this manganese(IV) complex was detected by mass spectroscopy under catalytic oxidation conditions.     

Olefin epoxidation by the hydrogen peroxide adduct of a novel non-heme mangangese(IV) complex: demonstration of oxygen transfer by multiple mechanisms

Olefin epoxidations are a class of reactions appropriate for the investigation of oxygenation processes in general. Here, we report the catalytic epoxidation of various olefins with a novel, cross-bridged cyclam manganese complex, Mn(Me2EBC)Cl2 (Me2EBC is 4,11-dimethyl-1,4,8,11-tetraazabicyclo[6.6.2]hexadecane), using hydrogen peroxide as the terminal oxidant, in acetone/water (ratio 4:1) as the solvent medium. Catalytic epoxidation studies with this system have disclosed reactions that proceed by a nonradical pathway other than the expected oxygen-rebound mechanism that is characteristic of high-valent, late-transition-metal catalysts. Direct treatment of olefins with freshly synthesized [Mn(IV)(Me2EBC)(OH)2](PF6)2 (pKa = 6.86) in either neutral or basic solution confirms earlier observations that neither the oxo-Mn(IV) nor oxo-Mn(V) species is responsible for olefin epoxidization in this case. Catalytic epoxidation experiments using the 18O labels in an acetone/water (H2(18)O) solvent demonstrate that no 18O from water (H2(18)O) is incorporated into epoxide products even though oxygen exchange was observed between the Mn(IV) species and H2(18)O, which leads to the conclusion that oxygen transfer does not proceed by the well-known oxygen-rebound mechanism. Experiments using labeled dioxygen, (18)O2, and hydrogen peroxide, H2(18)O2, confirm that an oxygen atom is transferred directly from the H2(18)O2 oxidant to the olefin substrate in the predominant pathway. The hydrogen peroxide adduct of this high-oxidation-state manganese complex, Mn(IV)(Me2EBC)(O)(OOH)+, was detected by mass spectra in aqueous solutions prepared from Mn(II)(Me2EBC)Cl2 and excess hydrogen peroxide. A Lewis acid pathway, in which oxygen is transferred to the olefin from that adduct, Mn(IV)(Me2EBC)(O)(OOH)+, is proposed for epoxidation reactions mediated by this novel, non-heme manganese complex. A minor radical pathway is also apparent in these systems.     

CO oxidation at nickel centres by N2O or O2 to yield a novel hexanuclear carbonate

Reaction of a nickel(0) carbonyl complex, K(2)[L(tBu)NiCO](2), with N(2)O generates a cyclic carbonate compound composed of six [Ni(II)(CO(3))K](+) units. The same product can also be obtained using O(2) as the oxidant in a solid-state/gas reaction. These conversions represent unique examples of a nickel-bound CO oxidation by N(2)O and O(2), respectively.     

Charge-transfer phase transition and zero thermal expansion in caesium manganese hexacyanoferrates

A series of caesium manganese hexacyanoferrates is prepared; Cs(I)(1.78)Mn(II)[Fe(II)(CN)6]0.78[Fe(III)(CN)6](0.22) (1), Cs(I)(1.57)Mn(II)[Fe(II)(CN)6]0.57[Fe(III)(CN)6](0.43) (2), Cs(I)(1.51)Mn(II)[Fe(II)(CN)6]0.51[Fe(III)(CN)6](0.49) (3), and Cs(I)(0.94)Mn(II)[Fe(II)(CN)6]0.21[Fe(III)(CN)6](0.70).0.8H2O (4). 1-3 show charge-transfer phase transitions between the high-temperature (HT) and low-temperature (LT) phases with transition temperatures (T(1/2 downward arrow), T(1/2 upward arrow)) of (207 K, 225 K) (1), (190 K, 231 K) (2), and (175 K, 233 K) (3) at a cooling and warming rates of 0.5 K min(-1). Variable temperature IR spectra indicate that the valence states of the LT phases of 1-3 are Cs(I)(1.78)Mn(II)(0.78)Mn(III)(0.22)[Fe(II)(CN)6], Cs(I)(1.57)Mn(II)(0.57)Mn(III)(0.43)[Fe(II)(CN)6], and Cs(I)(1.51)Mn(II)(0.51)Mn(III)(0.49) [Fe(II)(CN)6], respectively. The XRD measurements for 1-3 show that crystal structures of the HT and LT phases are cubic structures (Fm3[combining macron]m), but the lattice constants decrease from the HT phase to the LT phase; a = 10.5446(17) --> 10.4280(7) A (1), 10.5589(17) --> 10.3421(24) A (2), and 10.5627(11) --> 10.3268(23) A (3). The magnetization vs. temperature curves and the magnetization vs. external magnetic field curves show that the LT phases are ferromagnetic with Curie temperatures of 4.3 (1), 5.0 (2), and 5.6 K (3). At a cooling rate of -0.5 K min(-1), 4 does not show the charge-transfer phase transition, but does show a behavior of zero thermal expansion with a thermal expansivity of +0.2 x 10(-6) K(-1) throughout the temperature range 300 and 20 K.     

Self-assembly of D-penicillaminato M6M'8 (M = Ni(II), Pd(II), Pt(II); M' = Cu(I), Ag(I)) clusters and their organization into extended La(III)M6M'8 supramolecular structures

A series of chiral M(6)M'(8) cluster compounds having twelve free carboxylate groups, [M(6)M'(8)(D-pen-N,S)(12)X](5-) (M/M'/X = Pd(II)/Ag(I)/Cl(-) ([1](5-)), Pd(II)/Ag(I)/Br(-) ([2](5-)), Pd(II)/Ag(I)/I(-) ([3](5-)), Ni(II)/Ag(I)/Cl(-) ([4](5-)), Pt(II)/Ag(I)/Cl(-) ([5](5-)), Pd(II)/Cu(I)/Cl(-) ([6](5-)); D-H(2)pen = D-penicillamine), in which six cis-[M(D-pen-N,S)(2)](2-) square-planar units are bound to a [M'(8)X](7+) cubic core through sulfur-bridges, was synthesized by the reactions of cis-[M(D-pen-N,S)(2)](2-) with M' in water in the presence of halide ions. These M(6)M'(8) clusters readily reacted with La(3+) in aqueous buffer to form La(III)(2)M(6)M'(8) heterotrimetallic compounds, La(2)[1](CH(3)COO), La(2)[2](CH(3)COO), La(2)[3](CH(3)COO), La(2)[4](CH(3)COO), La(2)[5](CH(3)COO) and La(2)[6]Cl, in which the M(6)M'(8) cluster units are linked by La(3+) ions through carboxylate groups in a 1?:?2 ratio. While the La(III)(2)M(6)Ag(I)(8) compounds derived from [1](5-), [2](5-), [3](5-), [4](5-) and [5](5-) have a 1D helix supramolecular structure with a right-handedness, the La(III)(2)Pd(II)(6)Cu(I)(8) compound derived from [6](5-) has a 2D sheet-like structure with a triangular grid of the Pd(II)(6)Cu(I)(8) cluster units. When aqueous HCl was added to the reaction solution of [6](5-) and La(3+), another La(III)(2)Pd(II)(6)Cu(I)(8) heterotrimetallic compound, La(2)[6]Cl·HCl, in which the Pd(II)(6)Cu(I)(8) cluster units are linked by La(3+) ions to form a 2D structure with a rectangular grid, was produced. The solid-state structures of these La(III)(2)M(6)M'(8) compounds, determined by single-crystal X-ray crystallography, along with the spectroscopic properties of the M(6)M'(8) cluster compounds in solution, are described.     

(Ph)3PBr][Br7], [(Bz)(Ph)3P]2[Br8], [(n-Bu)3MeN]2[Br20], [C4MPyr]2[Br20], and [(Ph)3PCl]2[Cl2I14]: extending the horizon of polyhalides via synthesis in ionic liquids

The five polyhalides [(Ph)(3)PBr][Br(7)], [(Bz)(Ph)(3)P](2)[Br(8)], [(n-Bu)(3)MeN](2)[Br(20)], [C(4)MPyr](2)[Br(20)] ([C(4)MPyr] = N-butyl-N-methylpyrrolidinium), and [(Ph)(3)PCl](2)[Cl(2)I(14)] were prepared by the reaction of dibromine and iodine monochloride in ionic liquids. The compounds [(Ph)(3)PBr][Br(7)] and [(Bz)(Ph)(3)P](2)[Br(8)] contain discrete pyramidal [Br(7)](-) and Z-shaped [Br(8)](2-) polybromide anions. [(n-Bu)(3)MeN](2)[Br(20)] and [C(4)MPyr](2)[Br(20)] exhibit new infinite two- and three-dimensional polybromide networks and contain the highest percentage of dibromine ever observed in a compound. [(Ph)(3)PCl](2)[Cl(2)I(14)] also consists of a three-dimensional network and is the first example of an infinite polyiodine chloride. All compounds were obtained from ionic liquids as the solvent that, on the one hand, guarantees for a high stability against strongly oxidizing Br(2) and ICl and that, on the other hand, reduces the high volatility of the molecular halogens.