Bending, twisting, and breaking CuCN chains to produce framework materials: the reactions of CuCN with alkali-metal halides

The reactions of the low-temperature polymorph of copper(I) cyanide (LT-CuCN) with concentrated aqueous alkali-metal halide solutions have been investigated. At room temperature, KX (X = Br and I) and CsX (X = Cl, Br, and I) produce the addition products K[Cu-2(CN)(2)Br](H2O)-H-. (I), K-3[Cu-6(CN)(6)I-3](.)2H(2)O (II), Cs[Cu-3(CN)(3)Cl] (III), Cs[Cu-3(CN)(3)Br] (IV), and Cs-2[Cu-4(CN)(4)I-2](H2O)-H-. (V), with 3-D frameworks in which the -(CuCN)- chains present in CuCN persist. No reaction occurs, however, with NaX (X = Cl, Br, I) or KCl. The addition compounds, I-V, reconvert to CuCN when washed. Both low- and high-temperature polymorphs of CuCN (LT- and HT-CuCN) are produced, except in the case of Cs[Cu-3(CN)(3)Cl] (III), which converts only to LT-CuCN. Heating similar AX-CuCN reaction mixtures under hydrothermal conditions at 453 K for 1 day produces single crystals of I-V suitable for structure determination. Under these more forcing conditions, reactions also occur with NaX (X = Cl, Br, I) and KCl. NaBr and KCl cause some conversion of LT-CuCN into HT-CuCN, while NaCl and NaI, respectively, react to form the mixed-valence Cu(I)/Cu(II) compounds [Cu-II(OH2)(4)][Cu-4(I)(CN)(6)], a known phase, and [Cu-II(OH2)(4)][Cu-4(I)(CN)(4)I-2] (VI), a 3-D framework, which contains infinite -(CuCN)- chains. After 3 days of heating under hydrothermal conditions, the reaction between KI and CuCN produces [Cu-II(OH2)(4)][Cu-2(I)(CN)I-2](2) (VII), in which the CuCN chains are broken into single Cu-CN-Cu units, which in turn are linked into chains via iodine atoms and then into layers via long Cu-C and Cu-Cu interactions.

An investigation of the hydrogen glow discharge as a means of reducing metal halides /

"Contract AT-30-1-Gen-366."

Diffusive transport properties in monovalent and divalent metal-ion halide melts: A computer simulation study

Self- and cross-velocity correlation functions and related transport coefficients of molten salts are studied by molecular-dynamics simulation. Six representative systems are considered, i.e., NaCl and KCl alkali halides, CuCl and CuBr noble-metal halides, and SrCl2 and ZnCl2 divalent metal-ion halides. Computer simulation results are compared with experimental self-diffusion coefficients and electrical conductivities. Special attention is paid to dynamic cross correlations and their dependence on the Coulomb interactions as well as on the size and mass differences between anions and cations.

A fast atom bombardment mass spectrometry study of tris (3, 6-dioxaheptyl) amine-alkali metal halide complexes and hydrogen bonded complexes

The objective of this thesis was to demonstrate the potential of fast atom bombardment mass spectrometry (FABMS) as a probe of condensed phase systems and its possible uses for the study of hydrogen bonding. FABMS was used to study three different systems. The first study was aimed at investigating the selectivity of the ligand tris(3,6-dioxaheptyl) amine (tdoha) for the alkali metal cations. FABMS results correlated well with infrared and nmr data. Systems where a crown ether competed with tdoha for a given alkali metal cation were also investigated by fast atom bombardment. The results were found to correlate with the cation affinity of tdoha and the ability of the crown ether to bind the cation. In the second and third studies, H-bonded systems were investigated. The imidazole-electron donor complexes were investigated and FABMS results showed the expected H-bond strength of the respective complexes. The effects of concentration, liquid matrix, water content, deuterium exchange, and pre-ionization of the complex were also investigated. In the third system investigated, the abundance of the diphenyl sulfone-ammonium salt complexes (presumably H-bonded) in the FABMS spectrum were found to correlate with qualitative considerations such as steric hindrance and strength of ion pairs.

Mass spectrometric studies on aryltin compounds and alkali halides /

The fragmentation behavior of aryltin compounds [(p-ThAnis)nSnPh4.n (n=l-4); (p-ThAnis)3SnX (X=C1, Br, I); (o-CH30C6H4)3SnCl; Ph3Sn(o-pyr)] have been studied comparatively under EI and FAB ionization modes. Alkali halides were run under FAB mode. For the aryltin compounds, the effect of ligand type on the spectra have been explored in both EI and FAB modes. The fragmentation mechanisms have been examined with linked scans, such as fragment ion scans (B/E) and parent ion scans (B^/E). Ab Initio molecular orbital calculations were used to determine the structures of the fragments by comparing their relative stabilities. In the EI MS studies, negative ion EI mode has also been used for some of the aryltin compounds, to examine the possible ion molecule reactions under low pressures at 70eV. In the positive ion FAB MS studies, matrix optimization experiments have been carried out. Negative ion FAB experiments of all the compounds have been done in two different ways. Finally, the comparison of the two methods, EI MS and FAB MS, have been made.For alkali halides, the studies focused on the FAB MS behavior under different conditions. The intensities of cluster ions were reported, and the anomalies in the intensity distribution was also discussed.

Studies on some Metal Complexes of Dithio Ligands

The thesis deals with our studies on the synthesis and elucidation of structure of some metal complexes of dithio ligands, such as the dithiocarbamates, xanthates and 2-aminocyclopent-1-ene-1-dithiocarboxylate and its N-alkyl derivatives.2-Aminocyclopent-1-ene-1-dithiocarboxylate (ACDA) is an interesting ligand, because of its potential dual capability of bonding between the metal and the ligand. Since the earlier reports on the complexes of ACDA contain contradictory ideas on the nature of its bonding, it was thought worthwhile to undertake a detailed and systematic study of these type of complexes. As the ACDA complexes have very low solubilities in solvents like chloroform, we have used the isopropyl derivative of ACDA as the ligand. The increased solubility of these complexes have made it possible to investigate their NMR and solution electronic spectra.The complexes of this ligand have not yet been reported in the literature.We have synthesised some new mixed ligand complexes of dithiocarbamates by reacting bis(dithiocarbamato)-µ-dichloro dicopper complexes (obtained by the reaction of mixed benzoic dithiocarbamic anhydride and copper(II) chloride) with ACDA or its N-alkyl derivatives.Interactions of metal halides with the mixed anhydrides formed from benzoylchloride and xanthates have also been investigated. Novel complexes of the type, [Cu2(RXant)CI] (R=i-Bu, i-Pr, n-Bu or n-Pr)) have been isolated from the reaction of copper(II) chloride and the mixed anhydride, and these reactions appear to be like the clock reactions reported in the literature.It also deal with the characterisation of the complexes of the type [Hg(R2d t c )X] (X=Cl, Br or 1),[Cu3(R2dtc)6][Cu2Br6] and [Cu(R2dtc)Cl2](R2=Me2,Et2,Pip,Morph or Pyrr)respectively, synthesised by simple and novel routes, different from those reported earlier.

Diffusive transport properties in monovalent and divalent metal-ion halide melts: A computer simulation study

Self- and cross-velocity correlation functions and related transport coefficients of molten salts are studied by molecular-dynamics simulation. Six representative systems are considered, i.e., NaCl and KCl alkali halides, CuCl and CuBr noble-metal halides, and SrCl2 and ZnCl2 divalent metal-ion halides. Computer simulation results are compared with experimental self-diffusion coefficients and electrical conductivities. Special attention is paid to dynamic cross correlations and their dependence on the Coulomb interactions as well as on the size and mass differences between anions and cations.

Tris(trimethylsilyl)silyl substituted alkali- and transition metal guaiazulenides

In der vorliegenden Arbeit wird ein prochirales, aus natürlichen Resourcen gewonnenes Azulen, das Guajazulen genutzt, um neuartige chirale Cyclopentadienyl-Systeme aufzubauen. Mit Alkalimetallhypersilaniden als starke und sperrige Nukleophile gelingt es hypersilylsubstituierte Gujazulenide zu synthetisieren. Diese wurden mittels Elementaranalyse, NMR-Spektroskopie und Röntgendiffraktometrie charakterisiert. Durch nachfolgende Metathesen mit Übergangsmetallhalogeniden konnten in vielen Fällen die entsprechenden Metallocene erhalten werden. Die Experimente enthüllen eine ausgeprägte Regioselektivität der Addition des sperrigen Hypersilyanions an das Guajazulen, die durch das eingesetzte Lösungsmittel graduell verändert werden kann. In nicht-koordinierenden Lösungsmitteln findet man ausschließlich eine Addition an der 6-Position, die 6-Hypersilyl-2,6-dihydroguajazulenide (6-Hyp-Hgual) (M=Li 1, K 2, Cs 4) in ausgezeichneten Ausbeuten liefert. In polaren Solventien erhält man hingegen Mischungen der 6- und 8-Regioisomeren: 2 bzw. (8-Hyp-Hgual) (3). 2 bleibt aber hierbei das Hauptprodukt. Röntgenbeugungsexperimente zeigen, dass 1 im Kristall als dimerer Sandwich-Komplex, meso-[Li2(6-Hyp-Hgual)2], und die THF-Solvate (thf)4K(6-Hyp-Hgual) (2a) sowie (thf)4K(8-Hyp-Hgual) (3a) jeweils als Halb-Sandwich-Komplexe in einer racemischen Mischung vorliegen. Die Verbindungen 1, 2, 3 and 4 eignen sich sehr gut dazu, in Metathesereaktionen als Precursor für neuartige chirale Metallozen-Komplexe eingesetzt zu werden. Insbesondere das Kaliumderivat 2 besticht durch die einfache und relativ preiswerte Synthese, die erzielten hohen Ausbeuten (>80%) und seine leichte Handhabbarkeit. In THF als Solvent wurden die Metallocene 5:5-M’(6-Hyp-Hgual)2 (M’ = Mn 5, Fe 6, Ni 8) und 5:5-Fe(8-Hyp-Hgual)2 (7) erhalten. Bei Verwendung einiger redox-aktiver Metallhalogenide beobachtet man jedoch die Zersetzung der Metallocene unter Bildung des oxidativen Kopplungsproduktes (3-Hyp-6-Hgual)2 (9) sowie der Ausscheidung von Metall. Die Umsetzung von Halogeniden der Gruppe 4 (TiCl3 and M’’Cl4 (M’’ = Ti, Zr, Hf)) mit 2 liefert in THF ausschließlich die Metallozendichloride M’’(6-Hyp-Hgual)2Cl2 (M’’ = Ti (10), Zr (11), Hf (12)). Die erhaltenen Metallozenderivate fallen als Diastereomeren-Gemische an, die sich durch fraktionierende Kristallisation teilweise oder vollständig in ihre Bestandteile, das jeweilige R,R-Racemat und das R,S-meso-Diastereomer auftrennen lassen. Die Strukturen der rac-Diastereomere konnten durch Beugungsexperimente aufgeklärt werden. Durch eine Metathese von 2 mit Hyp-Cl kann eine zweite Hypersilylgruppe in die 2-Position des Guajazulen-Gerüstes eingeführt werden. Das entstehende 2,6-bis(Hyp)-H2gua (14) kann anschließend mit nBuLi in das extrem luft- und feuchtigkeitsempfindliche Li[2,6-bis(Hyp)-Hgual] (15) überführt werden, dass wie 1 eine dimere Sandwich-Struktur aufweist. Durch Einführung des zweiten Hypersilylrestes werden die chemischen Eigenschaften des Azulenids dramatisch verändert. Während Verbindung 1 sich als guter Precursor für Metallocene erwies, gelang es uns bislang nicht, entsprechende Derivate der Verbindung 15 zu isolieren.

Theoretical and Experimental Studies in Nuclear Magnetic Resonance

Nuclear magnetic resonance (NMR) is a tool used to probe the physical and chemical environments of specific atoms in molecules. This research explored small molecule analogues to biological materials to determine NMR parameters using ab initio computations, comparing the results with solid-state NMR measurements. Models, such as dimethyl phosphate (DMP) for oligonucleotides or CuCl for the active site of the protein azurin, represented computationally unwieldy macromolecules. 31P chemical shielding tensors were calculated for DMP as a function of torsion angles, as well as for the phosphate salts, ammonium dihydrogen phosphate (ADHP), diammonium hydrogen phosphate, and magnesium dihydrogen phosphate. The computational DMP work indicated a problem with the current standard 31P reference of 85% H3PO4(aq.). Comparison of the calculations and experimental spectra for the phosphate salts indicated ADHP might be a preferable alternative as a solid state NMR reference for 31P. Experimental work included magic angle spinning experiments on powder samples using the UNL chemistry department’s Bruker Avance 600 MHz NMR to collect data to determine chemical shielding anisotropies. For the quadrupolar nuclei of copper and scandium, the electric field gradient was calculated in diatomic univalent metal halides, allowing determination of the minimal level of theory necessary to compute NMR parameters for these nuclei.

Reaktionen monovalenter Münzmetalle in flüssigem Ammoniak

Im Rahmen dieser Arbeit konnten erstmals eine Reihe von Ammoniakaten von Münzmetallhalogeniden (M(I)Hal) und Pseudohalogeniden aus flüssigem Ammoniak in einkristalliner Form isoliert und strukturell charakterisiert werden. Mit dem Ammoniakat des Gold(I)-iodids wurden Metathesen in flüssigem Ammoniak durchgeführt, die die Isolierung einiger sehr thermolabiler, teilweise explosiver Alkoholate des Golds ermöglichten. Die Bestimmung der Kristallstruktur eines Gold(I)-phenolates erlaubte erste Einblicke in deren Aufbau.rnIn der Reihe der Ammoniakate der M(I)Hal mit Ausnahme von Silberiodid, werden keine direkten Metall-Halogen-Kontakte ausgebildet. Die Ammoniakate der Chloride und Bromide des Kupfers und Silbers sowie des Kupferiodids besitzen isotype Strukturen. Sie liegen als Trisammoniakate [M(NH3)3]Hal vor. Im Ammoniakat von Silberiodid besitzen die Silberionen durchgängig die Koordinationszahl 4. Neben Ag•••NH3- findet man auch direkte Kationen-rnAnionen-Kontakte und sehr kurze Ag(I)-Ag(I)-Abstände. Das Goldkation im Ammoniakat von Goldiodid besitzt die Koordinationszahl 2 und wird ausschließlich durch Ammoniakmoleküle koordiniert. Die gebildeten H3N-NH3-Hanteln werden über aurophile Wechselwirkungen verknüpft.rn rnDie Ammoniakate der Cyanide von Silber und Gold, enthalten molekulare Baueinheiten des Typs:(H3N)nMCN [(n= 1 für M= Au und n= 2 für M= Ag].rnrnAnders als bei den solvatfreien Homologen wird eine Ausbildung von Polymerketten nicht beobachtet. Das linear aufgebaute Ammoniakat von Goldcyanid ermöglicht die Ausbildung von aurophilen Wechselwirkungen. Metallophile Wechselwirkungen zwischen dem als Dimer vorliegenden Ammoniakat von AgCN scheinen nicht ausgebildet zu werden.rnrnMetatheseversuche von Goldiodid mit einem Amid und diversen Alkanolaten lieferten teilweise explosive Produkte. Es ist davon auszugehen, dass mit zunehmender Basizität der eingesetzten Anionen, die an das Gold(I)-ion koordinierten Ammoniakmoleküle deprotoniert werden und explosives Goldamid gebildet wird. Der als zweites Produkt entstehende Alkohol kann ebenfalls ein Ammoniakat bilden. Im Fall von Li-Fencholat wird ein solches in Form sehr tiefschmelzender Einkristalle erhalten.rnrnDa die Deprotonierung der an Gold koordinierten Ammoniakmoleküle unweigerlich zu explosiven oder sehr instabilen Produkten führt, wurde die geringere Basizität der Phenolate ausgenutzt, um dies zu umgehen. Im Falle der Umsetzung von AuI mit Li-2,6-di-tert.-butylphenolat gelang tatsächlich die Isolierung eines kristallinen Gold(I)-phenolats.rn

Laser IInduced Liinear and Nonlliinear Optiicall Studiies on Certaiin Metall Halliides and Tartrate Crystalls ffor Photoniic Applliicatiions

Nonlinear optics is a broad field of research and technology that encompasses subject matter in the field of Physics, Chemistry, and Engineering. It is the branch of Optics that describes the behavior of light in nonlinear media, that is, media in which the dielectric polarization P responds nonlinearly to the electric field E of the light. This nonlinearity is typically only observed at very high light intensities. This area has applications in all optical and electro optical devices used for communication, optical storage and optical computing. Many nonlinear optical effects have proved to be versatile probes for understanding basic and applied problems. Nonlinear optical devices use nonlinear dependence of refractive index or absorption coefficient on the applied field. These nonlinear optical devices are passive devices and are referred to as intelligent or smart materials owing to the fact that the sensing, processing and activating functions required for optical processes are inherent to them which are otherwise separate in dynamic devices.The large interest in nonlinear optical crystalline materials has been motivated by their potential use in the fabrication of all-optical photonic devices. Transparent crystalline materials can exhibit different kinds of optical nonlinearities which are associated with a nonlinear polarization. The choice of the most suitable crystal material for a given application is often far from trivial; it should involve the consideration of many aspects. A high nonlinearity for frequency conversion of ultra-short pulses does not help if the interaction length is strongly limited by a large group velocity mismatch and the low damage threshold limits the applicable optical intensities. Also, it can be highly desirable to use a crystal material which can be critically phasematched at room temperature. Among the different types of nonlinear crystals, metal halides and tartrates have attracted due to their importance in photonics. Metal halides like lead halides have drawn attention because they exhibit interesting features from the stand point of the electron-lattice interaction .These materials are important for their luminescent properties. Tartrate single crystals show many interesting physical properties such as ferroelectric, piezoelectric, dielectric and optical characteristics. They are used for nonlinear optical devices based on their optical transmission characteristics. Among the several tartrate compounds, Strontium tartrate, Calcium tartrate and Cadmium tartrate have received greater attention on account of their ferroelectric, nonlinear optical and spectral characteristics. The present thesis reports the linear and nonlinear aspects of these crystals and their potential applications in the field of photonics.

Estimating the value of the metal-ligand bond dissociation enthalpy<D> (M-L) for adducts using empirical equations supported by TG data

In this work is presented and tested (for 106 adducts, mainly of the zinc group halides) two empirical equations supported in TG data to estimate the value of the metal-ligand bond dissociation enthalpy for adducts: <D> (M-O) = t i / g if t i < 420 K and <D> (M-O) = (t i / g ) - 7,75 . 10-2 . t i if t i > 420 K. In this empirical equations, t i is the thermodynamic temperature of the beginning of the thermal decomposition of the adduct, as determined by thermogravimetry, andg is a constant factor that is function of the metal halide considered and of the number of ligands, but is not dependant of the ligand itself. To half of the tested adducts the difference between experimental and calculated values was less than 5%. To about 80% of the tested adducts, the difference between the experimental (calorimetric) and the calculated (using the proposed equations) values are less than 15%.

Comparative electron impact and fast atom bombardment mass spectrometric studies of some HMPA adducts of phenyltin and phenyllead halides and studies of strong hydrogen bonding by FAB-MS

The fragmentation patterns and mass spectra of some phenyl tin and -lead halide adducts with hexamethylphosphoramide are compared by subjecting them t~ electron impact and fast atom bombardment ionization in a mass spectrometer. This comparison is restricted to the metal-containing ions. Ligand-exchange mechanisms of some of the metal-containing species are explored by FAB-MS. Several moisturesensitive organo-metallics and H-bonded systems have been examined by FAB for attempted characterization, but without any success. Scavenging and trapping of water molecules by complex aggregates in solutions of quaternary ammonium fluorides and hydroxides are investigated by FAB to complement previous NMR-studies.