Crystal and molecular structures of alkali- and alkaline-earth-metal complexes of N,N-dimethylformamide

Structures of lithium, sodium, magnesium, and calcium complexes of NJ-dimethylformamide (DMF) have been investigated by X-ray crystallography. Complexes with the formulas LiCl.DMF.1/2H20, NaC104.2DMF, CaC12.2DMF.2H20, and Mg(C104)2.6DMF crystallized in space groups P2]/c, P2/c, Pi, and Ella, respectively, with the following cell dimensions: Li complex, a = 13.022 (7) A, b = 5.978 (4) A, c = 17.028 (10) A, = 105.48 (4)O, Z = 8; Na complex, a = 9.297 (4)A, b = 10.203 (3) A, c = 13.510 (6) A, /3 = 110.08 (4)O, Z = 4; Ca complex, a = 6.293 (4) A, b = 6.944 (2) A, c = 8.853(5) A, a = 110.15 (3)O, /3 = 105.60 (6)", y = 95.34 (5)", Z = 1; Mg complex, a = 20.686 (11) A, b = 10.962 (18) A,c = 14.885 (9) A, /3 = 91.45 (5)O, Z = 4. Lithium is tetrahedrally coordinated while the other three cations are octahedrally coordinated; the observed metal-oxygen distances are within the ranges generally found in oxygen donor complexes of these metals. The lithium and sodium complexes are polymeric, with the amide and the anion forming bridging groups between neighboring cations. The carbonyl distances become longer in the complexes accompanied by a proportionate decrease in the length of the central C-N bond of the amide; the N-C bond of the dimethylamino group also shows some changes in the complexes. The cations do not deviate significantly from the lone-pair direction of the amide carbonyl and remain in the amide plane. Infrared spectra of the complexes reflect the observed changes in the amide bond distances.

Novel Oxidation of Pyridoxal in Ternary Metal Complexes. An X-Ray Study of the Products

Attempts to prepare ternary metal complexes of pyridoxylidene-amino acid Schiff bases culminated in the oxidation of pyridoxal to pyridoxic acid or to its lactone and their complex formation, as evidenced from an X-ray study.

Polymerization of Ethene and Branched α-olefins with Group IV Metal Complexes Bearing Nitrogen- and Oxygen-Based Ligands

The commodity plastics that are used in our everyday lives are based on polyolefin resins and they find wide variety of applications in several areas. Most of the production is carried out in catalyzed low pressure processes. As a consequence polymerization of ethene and α-olefins has been one of the focus areas for catalyst research both in industry and academia. Enormous amount of effort have been dedicated to fine tune the processes and to obtain better control of the polymerization and to produce tailored polymer structures The literature review of the thesis concentrates on the use of Group IV metal complexes as catalysts for polymerization of ethene and branched α-olefins. More precisely the review is focused on the use of complexes bearing [O,O] and [O,N] type ligands which have gained considerable interest. Effects of the ligand framework as well as mechanical and fluxional behaviour of the complexes are discussed. The experimental part consists mainly of development of new Group IV metal complexes bearing [O,O] and [O,N] ligands and their use as catalysts precursors in ethene polymerization. Part of the experimental work deals with usage of high-throughput techniques in tailoring properties of new polymer materials which are synthesized using Group IV complexes as catalysts. It is known that the by changing the steric and electronic properties of the ligand framework it is possible to fine tune the catalyst and to gain control over the polymerization reaction. This is why in this thesis the complex structures were designed so that the ligand frameworks could be fairly easily modified. All together 14 complexes were synthesised and used as catalysts in ethene polymerizations. It was found that the ligand framework did have an impact within the studied catalyst families. The activities of the catalysts were affected by the changes in complex structure and also effects on the produced polymers were observed: molecular weights and molecular weight distributions were depended on the used catalyst structure. Some catalysts also produced bi- or multi-modal polymers. During last decade high-throughput techniques developed in pharmaceutical industries have been adopted into polyolefin research in order to speed-up and optimize the catalyst candidates. These methods can now be regarded as established method suitable for both academia and industry alike. These high-throughput techniques were used in tailoring poly(4-methyl-1-pentene) polymers which were synthesized using Group IV metal complexes as catalysts. This work done in this thesis represents the first successful example where the high-throughput synthesis techniques are combined with high-throughput mechanical testing techniques to speed-up the discovery process for new polymer materials.

Schiff Base Complexes and their Assemblies on Surfaces

Schiff bases and their transition metal complexes are of significant current interest even though they have been prepared for decades. They have been used in various applications such as catalysis, corrosion protection, and molecular sensors. In this study, N-aryl Schiff base ketimine ligands as well as numerous new, differently substituted salen and salophen-type ligands and their cobalt(II), copper(II), iron(II), manganese(II), and nickel(II) complexes were synthesised. New solid state structures of the above compounds and the dioxygen coordination properties of cobalt(II) complexes and catalytic properties of three synthesised binuclear complexes were examined. The prepared complexes were applied in the formation of self-assembled layers on a polycrystalline gold surface and liquid-graphite interface. The effect of metal ion and ligand structure on the as-formed patterns was studied. When studying gold surfaces, a unique thiol-assisted dissolution of elemental gold was observed and a new thin gold foil preparation method was introduced. In the summary, synthesis, structures, and properties of Schiff base ligands and their transition metal complexes are described in detail and the applications of these reviewed. Assemblies of other complexes on a liquid-graphite interface and on a gold surface are also presented, and the surface characterisation methods and surfaces employed are described.

Polymer supported metal complexes as catalysts for oxidation of thiosalts by molecular oxygen IV. Quaternised poly(4-vinyl pyridine) complexes with Cu2+ as template

Copper(II) complexes of quaternised poly(4-vinylpyridine) (PVP) of different degrees of quaternisation and copper content have been prepared by crosslinking the polymer with 1,2-dibromoethane in the presence of Cu2+ ion as template. The stability constant of the PVP---Cu(II) complexes is found to increase with the degree of crosslinking quaternisation of the resin, but the rate at which Cu2+ is adsorbed by the resin decreases. An optimum combination of both stability and rate can be achieved with a moderate degree (31%) of crosslinking. A kinetic study reveals that quaternisation increases significantly the catalytic activity of the complex for the oxidation of S2O2−3 by O2 compared with PVP----Cu(II) without quaternisation, but it deactivates the complex for the oxidation of both S3O2−6 and S4O2−6. The batch reactor oxidation kinetics at pH 2.16, where the rate is observed to be maximum, is well explained by the Langmuir—Hinshelwood model assuming the coordination of both O2 and thioanion to Cu(II) as a precursor to the oxidation reaction.

Rare earth transition metal sulfides, LnMS3

Ternary rare earth transition metal sulfides LnMS3 with Ln = La, Nd, and Gd, and M = V and Cr; as well as Ln = La and M = Mn, Fe, Co, and Ni have been prepared and characterized. The vanadium and chromium sulfides crystallize in a monoclinic layer structure isotypic with LaCrS3, while the other LnMS3 sulfides crystallize in a hexagonal structure. Chemical shifts of the metal K-absorption edge and XPS binding energies of core levels indicate that the transition metal is trivalent in the V and Cr sulfides, while it is divalent in the Mn, Fe, Co, and Ni sulfides. Electrical and magnetic properties of the sulfides are discussed in terms of their structures and the electronic configurations of the transition metal ions.

Metal complexes of thiophene 2-thiocarboxamide. Proton and 13C NMR, IR and electronic spectral studies

The complexes of thiophene 2-thiocarboxamide (TTCA) with some metal chlorides and bromides [M = Ni(II), Zn(II), Cd(II), Hg(II) and Cu(I)] are described. Elemental analyses, magnetic susceptibilities and conductance studies, electronic, IR, proton and 13C magnetic resonance spectra are reported. The results suggest exclusive coordination of TTCA through the thiocarbonyl sulfur. The influence of the thiophene ring on the donor properties of the thioamide are discussed.

Crystal structure and semiconductor-metal transition of the quasi-two-dimensional transition metal oxide, La2NiO4

Abstract is not available.

Study of transition-metal monosulphides by photoelectron spectroscopy

Monosulphides of the first-row transition metals have been studied by X-ray and UV photoelectron spectroscopy. Systematics in the valence bands as well as metal and sulphur core levels across the series have been discussed. Exchange splittings and spin-orbit splittings in these compounds have been examined. CuS is found to show features of both S2 and S22.

Metal-Nucleotide Interactions: Crystal Structures of Alkali (Li+, Na+, K+) and Alkaline Earth (Ca2+, Mg2+) Metal Complexes of Adenosine 2'-Monophosphate

Crystal structures of lithium, sodium, potassium, calcium and magnesium salts of adenosine 2'-monophosphate (2'-AMP) have been obtained at atomic resolution by X-ray crystallographic methods. 2'-AMP.Li belongs to the monoclinic space group P21 with a = 7.472(3)Å, b = 26.853(6) Å, c = 9.184(1)Å, b = 113.36(1)Å and Z= 4. 2'-AMP.Na and 2'-AMP.K crystallize in the trigonal space groups P31 and P3121 with a = 8.762(1)Å, c = 34.630(5)Å, Z= 6 and a = 8.931(4), Åc = 34.852(9)Å and Z= 6 respectively while 2'-AMP.Ca and 2'-AMP.Mg belong to space groups P6522 and P21 with cell parameters a = 9.487(2), c = 74.622(13), Z = 12 and a = 4.973(1), b = 10.023(2), c = 16.506(2), beta = 91.1(0) and Z = 2 respectively. All the structures were solved by direct methods and refined by full matrix least-squares to final R factors of 0.033, 0.028, 0.075, 0.069 and 0.030 for 2'-AMP.Li, 2'-AMP.Na, 2'- AMP.K, 2'-AMP.Ca and 2'-AMP.Mg, respectively. The neutral adenine bases in all the structures are in syn conformation stabilized by the O5'-N3 intramolecular hydrogen bond as in free acid and ammonium complex reported earlier. In striking contrast, the adenine base is in the anti geometry (cCN = -156.4(2)°) in 2'-AMP.Mg. Ribose moieties adopt C2'-endo puckering in 2'-AMP.Li and 2'-AMP.Ca, C2'-endo-C3'-exo twist puckering in 2'-AMP.Na and 2'-AMP.K and a C3'-endo-C2'-exo twist puckering in 2'-AMP.Mg structure. The conformation about the exocyclic C4'-C5' bond is the commonly observed gauche-gauche (g+) in all the structures except the gauche- trans (g-) conformation observed in 2'-AMP.Mg structure. Lithium ions coordinate with water, ribose and phosphate oxygens at distances 1.88 to 1.99Å. Na+ ions and K+ ions interact with phosphate and ribose oxygens directly and with N7 indirectly through a water oxygen. A distinct feature of 2'-AMP.Na and 2'-AMP.K structures is the involvement of ribose O4' in metal coordination. The calcium ion situated on a two-fold axis coordinates directly with three oxygens OW1, OW2 and O2 and their symmetry mates at distances 2.18 to 2.42Å forming an octahedron. A classic example of an exception to the existence of the O5'-N3 intramolecular hydorgen bond is the 2'-AMP.Mg strucure. Magnesium ion forms an octahedral coordination with three water and three phosphate oxygens at distances ranging from 2.02 to 2.11Å. A noteworthy feature of its coordination is the indirect link with N3 through OW3 oxygen resulting in macrochelation between the base and the phosphate group. Greater affnity of metal clays towards 5' compared to 2' and 3' nucleotides (J. Lawless, E. Edelson, and L. Manring, Am. Chem. Soc. Northwest Region Meeting, Seattle. 1978) due to macrochelation infered from solution studies (S. S. Massoud, H. Sigel, Eur. J. Biochem. 179, 451-458 (1989)) and interligand hydrogen bonding induced by metals postulated from metal-nucleotide structures in solid state (V. Swaminathan and M. Sundaralingam, CRC. Crit. Rev. Biochem. 6, 245-336 (1979)) are borne out by our structures also. The stacking patterns of adenine bases of both 2'-AMP.Na and 2'-AMP.K structures resemble the 2'-AMP.NH4 structure reported in the previous article. 2'-AMP.Li, 2'-AMP.Ca and 2'-AMP.Mg structures display base-ribose O4' stacking. An overview of interaction of monovalent and divalent cations with 2' and 5'-nucleotides has been presented.

Generalized self-assembly of scalable two-dimensional transition metal oxide nanosheets

Two-dimensional (2D) transition metal oxide systems present exotic electronic properties and high specific surface areas, and also demonstrate promising applications ranging from electronics to energy storage. Yet, in contrast to other types of nanostructures, the question as to whether we could assemble 2D nanomaterials with an atomic thickness from molecules in a general way, which may give them some interesting properties such as those of graphene, still remains unresolved. Herein, we report a generalized and fundamental approach to molecular self-assembly synthesis of ultrathin 2D nanosheets of transition metal oxides by rationally employing lamellar reverse micelles. It is worth emphasizing that the synthesized crystallized ultrathin transition metal oxide nanosheets possess confined thickness, high specific surface area and chemically reactive facets, so that they could have promising applications in nanostructured electronics, photonics, sensors, and energy conversion and storage devices.

Unusual dielectric response in B-site size-disordered hexagonal transition metal oxides

We discover that hexagonal holmium copper titanate (Ho2CuTiO6), has a unique and highly desirable combination of high dielectric constant, low losses, very small temperature coefficient, and low frequency dependence. Our first-principles calculations indicate that these exceptional properties result from a size-difference at the Cu/Ti B-site that suppresses the expected ferroelectric transition, combined with the dominance of intermediate-frequency polar vibrational modes in the dielectric response. Our results suggest that the use of such B-site disorder in alloys of hexagonal transition-metal oxides should generally result in similar robust dielectrics.

Synthesis, Structure, and Magnetic Properties of Amine-Templated Transition-Metal Phosphites

Transition-metal phosphites of cobalt and vanadium, [C4N2H12][Co(HPO3)(2)] (I), [C4N2H14][Co(HPO3)(2)] (II), [Co[C4H8N12)(H2PO3)(2)] (III),[C4N2H14][(VF)-F-III(HPO3)(2)]center dot H2O (IV), and[C3N2H5](2)[V-4(III)(H2O)(3)(HPO3)(4)(HPO4)(3)] (V), have been synthesized and characterized. Organophosphorus esters were employed to stabilize cobalt in tetrahedral coordination and also to prepare the low-dimensional structures, which are otherwise difficult to synthesize. The structures have one- (I, II, IV), two- (III) and three-dimensionally (V) extended networks built up by the linking of metal polyhedra and phosphite units. Another vanadyl phosphite, [C2N2H10][((VO)-O-IV)(3)(H2O) (HPO3)(4)]center dot H2O,([15]) was also prepared and investigated extensively by ESR, magnetic susceptibility, and other studies. All the compounds in the present study exhibit antiferromagnetic interactions. Well-established magnetic models have been used to fit the experimental data. The compounds havealso been characterized in detail by using UV/Vis spectroscopic studies.