Coordination chemistry of the soluble metal oxide analogue [Mo5O13(OCH3)4(NO)]3- with manganese carbonyl species

The reactions of neutral or cationic manganese carbonyl species towards the oxo-nitrosyl complex [Na(MeOH)[Mo(5)O(13)(OCH(3))(4)(NO)]](2-) have been investigated in various conditions. This system provides an unique opportunity for probing the basic reactions involved in the preparation of solid oxide-supported heterogeneous catalysts, that is, mobility of transition-metal species at the surface and dissolution-precipitation of the support. Under nitrogen and in the dark, the reaction of in situ generated fac-[Mn(CO)(3)](+) species with (nBu(4)N)(2)[Na(MeOH)-[Mo(5)O(13)(OMe)(4)(NO)]] in MeOH yields (nBu(4)N)(2)[Mn(CO)(3)(H(2)O)[Mo(5)O(13)(OMe)(4)(NO)]] at room temperature, while (nBu(4)N)(3)[Na[Mo(5)O(13)(OMe)(4)(NO)](2)[Mn(CO)(3)](2)] is obtained under reflux. The former transforms into the latter under reflux in methanol in the presence of sodium bromide; this involves the migration of the fac-[Mn(CO)(3)](+) moiety from a basal kappa(2)O coordination site to a lateral kappa(3)O site. Oxidation and decarbonylation of manganese carbonyl species as well as degradation of the oxonitrosyl starting material and reaggregation of oxo(methoxo)molybdenum fragments occur in non-deareated MeOH, and both (nBu(4)N)(4)[Mn(H(2)O)(2)[Mo(5)O(16)(OMe)(2)](2)[Mn(CO)(3)](2)] and (nBu(4)N)(4)[Mn(H(2)O)(2)[Mo(5)O(13)(OMe)(4)(NO)](2)] as well as (nBu(4)N)(2)[MnBr[Mo(5)O(13)(OMe)(4)(NO)]] have been obtained in this way. The rhenium analogue (nBu(4)N)(2)[Re(CO)(3)(H(2)O)[Mo(5)O(13)(OMe)(4)(NO)]] has also been synthesized. The crystal structures of (nBu(4)N)(2)[Re(CO)(3)(H(2)O)[Mo(5)O(13)(OMe)(4)(NO)]], (nBu(4)N)(3)[Na[Mo(5)O(13)(OMe)(4)(NO)](2)[Mn(CO)(3)](2)], (nBu(4)N)(4)[Mn(H(2)O)(2)[Mo(5)O(16)(OMe)(2)](2)[Mn(CO)(3)](2)], (nBu(4)N)(4)[Mn(H(2)O)(2)[Mo(5)O(13)(OMe)(4)(NO)](2)] and (nBu(4)N)(2)[MnBr[Mo(5)O(13)(OMe)(4)(NO)]] have been determined.     

Beiträge zum thermischen Verhalten wasserfreier Phosphate. IX. Darstellung und Kristallstruktur von Cr6(P2O7)4. Ein gemischtvalentes Pyrophosphat mit zwei- und dreiwertigem Chrom

Contributions on the Thermal Behaviour of Anhydrous Phosphates. IX. Synthesis and Crystal Structure of Cr₆(P₂O₇)₄. A Pyrophosphate Containing Di- and Trivalent Chromium Cr₆(P₂O₇)₄ (Cr₂²⁺Cr₄³⁺(P₂O₇)₄) can be obtained reducing CrPO₄ by phosphorus (950°C, 48 h, 100 mg iodine as mineralizer). By means of chemical transport reactions (transport agent iodine; 1050 → 950°C) the compound has been separated from its neighbour phases (Cr₂P₂O₇, CrP₃O₉) and crystallized (greenish, transparent crystals; edge length up to 0.3 mm). The crystal structure of Cr₆(P₂O₇)₄ (Spcgrp.: P-1; z = 1; a = 4.7128(8) Å, b = 12.667(3) Å, c = 7.843(2) Å, α = 89.65(2)°, β = 92.02(2)°, γ = 90.37(2) has been solved and refined from single crystal data (2713 unique reflections, 194 parameter, R = 0.035). Cr²⁺ is surrounded by six oxygen atoms which occupy the corners of an elongated octahedron (4 × d^{Cr? O} ≈? 2.04 Å; 2 × d^{Cr? O} ≈? 2.62 Å). The Cr³⁺ ions are also coordinated octahedraly (1.930 Å ≤ d_{Cr? O} ≤ 2.061 Å). The crystallographically independent pyrophosphate groups show nearly eclipsed conformation. The bridging angles (P? O? P) are 136.5° and 138.9° respectively.     

A study of the new perovskite solid solution series SrFexRu1−xO3−y by ruthenium-99 and iron-57 Mössbauer spectroscopy

The magnetic and structural properties of the solid solution SrFe_xRu_1?xO_3?y (0 ? x ? 0.5) have been studied using ⁵⁷Fe and ⁹⁹Ru Mössbauer spectroscopy and other techniques. These phases, which are here reported for the first time, have a distorted perovskite structure. The iron substitutes exclusively as Fe³⁺ and thereby causes oxygen deficiency, but has little effect on the magnetic behaviour of the Ru⁴⁺ until x > 0.2, whereupon the metallic band system begins to revert to a localized electron structure. The properties of a sample with x = 0.3 are complex and intermediate in character. For x > 0.3 the oxygen deficiency is reduced by substantial oxidation to Ru⁵⁺ until at x = 0.5 the system corresponds to Sr₂Fe³⁺Ru⁵⁺O₆.     

Rapid separation of pharmaceutical enantiomers using electrokinetic chromatography with a novel chiral microemulsion

A novel oil-in-water microemulsion incorporating the chiral surfactant dodecoxycarbonylvaline (DDCV) was used to achieve the rapid enantiomeric separation of pharmaceutical drugs by electrokinetic chromatography (EKC). Incorporation of DDCV into a microemulsion resulted in an elution range more than double that provided the micellar form of the surfactant aggregate. Interestingly, for the same compounds the enantioselectivity provided by the chiral DDCV microemulsions ranged from 1.06-1.30 for the neutral and cationic drugs, which was slightly higher than that provided by chiral DDCV micelles. The use of a low surface tension oil (ethyl acetate) permitted a much lower concentration of chiral surfactant to be employed; this, together with the use of a zwitterionic buffer (ACES) resulted in a very low conductivity microemulsion that allowed a higher separation voltage to be utilized, resulting in rapid enantiomeric separations (< 8 min.). Mobility matching of the buffer cation(s) was used to improve peak shape and efficiencies. In our limited survey of the phase diagram, the optimum composition of the microemulsion buffer was 1.0% (w/v) DDCV (30 mM), 0.5% (v/v) ethyl acetate, 1.2% (v/v) 1-butanol and 50 mM ACES buffer at pH 7.     

Ab initio MRD-CI calculations for breaking a chemical bond in a molecule in a crystal or other solid environment. III. Me2N?NO2 decomposition of dimethylnitramine in a large crystalline environment

Recently we extended our strategy for MRD-CI (multireference double excitation-configuration interaction) calculations, based on localized/local orbitals and an “effective” CI Hamiltonian, for molecular decompositions of large molecules to breaking a chemical bond in a molecule in a crystalline or other solid environment. Our technique begins with an explicit quantum chemical SCF calculation for a reference molecule surrounded by a number of other molecules in the multipole environment of more distant neighbors. The resulting canonical molecular orbitals are then localized, and the localized occupied and virtual orbitals in the region of interest are included explicitly in the MRD-CI with the remainder of the occupied localized orbitals being folded into an “effective” CI Hamiltonian. The MRD-CI calculations are then carried out for breaking a bond in the reference molecule. This method is completely general in that the space treated explicitly, as well as the surrounding space, may contain voids, defects, deformations, dislocations, impurities, dopants, edges and surfaces, boundaries, etc. Dimethylnitramine is the smallest prototype of the energetic R₂N—NO₂ nitramines, such as the 6-member ring RDX or the 8-member ring HMX. Decomposition of energetic compounds is initiated in the solid by a breaking of the target bond. Thus, it is crucial to know the difference in energy between breaking a bond in an isolated energetic molecule versus in the molecule in a solid. In the present study, we have carried out MRD-CI calculations for the Me₂N—NO₂ dissociation of dimethylnitramine in a dimethylnitramine crystal. The cases we investigated were one dimethylnitramine molecule (surrounded by 53 and 685 neighboring dimethylnitramine molecules represented by multipoles), three dimethylnitramine molecules, and three dimethylnitramine molecules (surrounded by 683 neighbors). All multipoles were cumulative atomic multipoles up through quadrupoles. The MRD-CI calculations on dimethylnitramine required large numbers of reference configurations from which were allowed all single and double excitations.     

The Effect of Static Magnetic Fields on the Photohemolysis of Human Erythrocytes by Ketoprofen

Ultraviolet irradiation (λ > 300 nm) of the nonsteroidal anti-inflammatory agent ketoprofen (KP, 3-benzoyl-α-methylbenzoacetic acid) in aqueous solution, pH 7.4, results in heterolytic decarboxylation of the drug to give 3-ethylbenzophenone (EtBP). Ketoprofen caused the photohemolysis of human erythrocytes probably as a result of lipid peroxidation. Application of a static magnetic field (250–1500 G) during UV (>300 nm) irradiation of KP and erythrocytes significantly decreased the time required for photohemolysis. This observation suggests that KP-induced photohemolysis involves the initial generation of a triplet radical pair derived from the reaction of triplet state KP (or 3-EtBP) with erythrocyte component(s) probably lipids. The magnetic field increases the concentration and/or lifetime of free radicals that escape from the radical pair so that the critical radical concentration needed to initiate membrane damage and cause cell lysis is reached sooner. Spin-trapping studies with 2,6-dibromo-1-nitrosobenzene-4-sulfonate confirmed that the application of an external static magnetic field increased the concentration of radicals released during the photolysis of either KP or 3-EtBP dissolved in organized media such as sodium dodecylsulfate micelles.     

Asymmetric Synthesis of Calyculin C. 2. Synthesis of the C(26)-C(37) Fragment and Model Wittig Couplings

We report our synthesis of the C(26)-C(37) fragment of serine/threonine protein phosphatase PP1 and PP2A inhibitor calyculin C (1). Outlined in this paper are synthetic approaches to the two components based on disconnection at the C(33)-N(3) amide bond. We report the successful synthesis of the C(33)-C(37) aza-sugar derived from D-lyxose which was coupled onto a C(26)-C(32) aminooxazole originating from L-pyroglutamic acid. Elaboration of the resulting amide to a fully deprotected C(26)-C(37) fragment of calyculin C completed our synthesis. This provided an appropriate phosphonium salt for use in a Wittig olefination for joining both halves of the natural product.     

Structural similarities and differences among mixed-metal clusters containing a single M(PPh3) (M = Cu, Ag or Au) fragment

The heteronuclear metal clusters [H₃MRu₄(CO)₁₂(PPh₃)] and [MFe₃(μ-COMe)(CO)₁₀(PPh₃)] (M = Cu, Ag or Au) have been prepared; the gold-tetraruthenium cluster has a different metal core geometry to that adopted by the copper and silver analogues, whereas all three iron-Group IB mixed-metal clusters have the same geometry.     

Possible role of relativistic effects in the plasticity of the coordination geometry of cadmium(II). A voltammetric study of the stability of the complexes of cadmium(II) with 12-crown-4,15-crown-5 and 18-crown-6 in aqueous solution and the structures of [Cd(benzo-18-crown-6)(NCS)(2)] and [K(18-crown-6)][Cd(SCN)(3)

A differential pulse voltammetric study of complexes of Cd(II) and Pb(II) with crown ethers is reported. Measured log K(1) values for Cd(II) with 18-crown-6 (1,4,7,10,13,16-hexaoxacyclooctadecane), 15-crown-5 (1,4,7,10,13-pentaoxacyclopentadecane), and 12-crown-4 (1,4,7,10-tetraoxacyclododecane) are respectively 2.53 (+/-0.06), 1.97 (+/-0.07), and 1.72 (+/-0.08) and for Pb(II) with 18-crown-6 is 4.17 (+/-0.03), all at 25 degrees C in 0.1 M LiNO(3). Cd(II) is smaller than is usually associated with strong bonding with crown ethers. The high log K(1) values for Cd(2+) with crown ethers found here are discussed in terms of distortion of Cd(II) by relativistic effects. The resulting plasticity of the coordination geometry of the Cd(II) ion allows it to meet the metal ion size requirements of all the crown ethers, allowing high log K(1) values to occur. Crystal structures for [Cd(bz-18-crown-6)(SCN)(2)] (1) (bz-18-crown-6 = benzo-1,4,7,10,13,16-hexaoxacyclooctadecane) and [K(18-crown-6)][Cd(SCN)(3)] (2) are reported. 1 was triclinic, space group P1, a = 8.5413(2), b = 10.0389(2), and c = 13.4644(2) A, alpha = 94.424(1), beta = 102.286(1), and gamma = 93.236(1) degrees, Z = 2, and final R = 0.023. 2 was orthorhombic, space group Cmc2(1), a = 14.7309(3), b = 15.1647(3), and c = 10.6154(2) A, Z = 4, and final R = 0.020. In 1, the Cd occupies the cavity of the bz-18-crown-6 with long average Cd-O bond lengths of 2.65 A and is N-bonded to the thiocyanates with short average Cd-N bonds of 2.12 A. In [Cd(bz-18-crown-6)(SCN)(2)], the linear coordination involving the Cd and the two N-bonded thiocyanate groups in 1 is discussed in terms of the role of relativistic effects in the tendency to linear coordination geometry in group 12 metal ions. In 2 Cd forms a polymeric structure involving thiocyanate bridges between Cd atoms and K(+) occupies the cavity of the crown ether. 2 highlights the fact that cadmium is almost never S-bonded to thiocyanate except in bridging thiocyanates.     

Synthesis and reactivity of the monomeric late-transition-metal parent amido complex [Ir(Cp*)(PMe3)(Ph)(NH2)

The late-transition-metal parent amido compound [Ir(Cp*)(PMe3)(Ph)(NH2)] (2) has been synthesized by deprotonation of the corresponding ammine complex [Ir(Cp*)(PMe3)(Ph)(NH3)][OTf] (6) with KN(SiMe3)2. An X-ray structure determination has ascertained its monomeric nature. Proton-transfer studies indicate that 2 can successfully deprotonate p-nitrophenylacetonitrile, aniline, and phenol. Crystallographic analysis has revealed that the ion pair [Ir(Cp*)(PMe3)(Ph)(NH3)][OPh] (8) exists as a hydrogen-bonded dimer in the solid state. Reactions of 2 with isocyanates and carbodiimides lead to overall insertion of the heterocumulenes into the N--H bond of the Ir-bonded amido group, demonstrating the ability of 2 to act as an efficient nucleophile. Intriguing reactivity is observed when amide 2 reacts with CO or 2,6-dimethylphenyl isocyanide. eta4-Tetramethylfulvene complexes [Ir(eta4-C5Me4CH2)(PMe3)(Ph)(L)] (L=CO (15), CNC6H3-2,6-(CH3)2 (16)) are formed in solution through displacement of the amido group by the incoming ligand followed by deprotonation of a methyl group on the Cp* ring and liberation of ammonia. Conclusive evidence for the presence of the Ir-bonded eta4-tetramethylfulvene moiety in the solid state has been provided by an X-ray diffraction study of complex 16.