Thesis (D.A.)--University of Delaware, 2010. / Principal faculty advisor: Charles G. Riordan, Dept. of Chemistry & Biochemistry. Includes bibliographical references.

This work is predominantly devoted to the 4-phenylpyridine ligand and the role that it plays in the formation of a series of inorganic coordination complexes termed Werner Clathrates. The synthesis and characterization by single crystal X-ray diffraction techniques are reported for 18 structures, the majority of which, upon crystallization, have the ability to include solvent or guest molecules within the host framework. The compounds are divided into four broad classes with the host complex of each as follows: Class A [Ni(NCS)₂(4-PhPy)₄]; Class B [NiCl₂(4-PhPy)₄]; Class c [Ni(NCS)₂(4-MePy)₂(4-PhPy)₂]; Class D [NiX₂(dmso)₂(4-PhPy)₂] where X= Ncs- or Cland [Ni(NCS)₂(4-RPy)₄] where R = 4-t-Bu or 4-Bz. The guest molecules, anionic ligand and substituent on the pyridine ligand have all been varied to try to establish the role that they each play in the formation of a structure. Much effort has been spent on the location and refinement of disordered guest molecules. Use has been made of statistical disorder and molecular scattering factors to try and successfully model these guests. The shapes of the cavities containing the guest molecules have been mapped by volume calculations and comparisons made between the packing of the compounds. Several of the complexes pack in space groups which are subsets of others and attempts have been made to determine the cause of the reduction in symmetry. A new technique to analyze competition experiments, with two guest solvents competing for occupation of the voids within the host lattice, has been established. Preliminary results for competition between p-xylene/benzene, p-xylene/toluene and p-xylene/ethylbenzene with the host complex [Ni(NCS)₂(4-ViPy)₄] are reported. The ability of the host complex [Ni(NCS)₂(4-MePy)₂(4-PhPy)₂] to separate a series of straight chain alcohols is demonstrated. The preference, by this host complex, for guest molecules containing a linear skeleton of 5 non-hydrogen atoms, is explained in terms of potential energy and residual volume calculations. Thermal analysis, consisting of thermogravimetry and differential thermal analysis, has been performed on several of the compounds. Temperatures of guest release, host decomposition and the enthalpies involved at each of these steps are reported.

Includes bibliographical references. / Atomic diffusion during the solid state formation of thin films of nickel silicides (Ni2Si and NiSi) from nickel and amorphous silicon has been investigated using 31Si radioactive tracer and inert marker techniques. Samples were prepared by vacuum deposition of thin films of nickel and silicon, followed by thermal annealing to effect silicide growth. The radioactive tracer investigation of Ni2Si showed nickel to be the diffusing species during silicide growth. Sharply defined Ni2si* profiles of 100% radioactive concentration at the sample surface were - obtained. The results are compared with previous results in which the profiles were more spread out and of lower surface concentration. The radioactive tracer investigation of NiSi formation showed that nickel is also the diffusing species during second phase growth. The NiSi * layer was found to be of 100% concentration. Some spreading of the activity profile near the NiSi/NiSi* interface was observed. The results were consistent with previous 31Si tracer work on NiSi formation and also with the present Ni * 2Si results. The inert marker investigation used an ultra-thin (5-10 A) continuous layer of Mo or Ta to monitor atomic movement during silicide growth. The results confirmed nickel to be the diffusing species during the growth of both phases. These results are in excellent agreement with previous inert marker studies of nickel silicide growth.

A pyridine-containing Schiff base complex, 2, 12-dimethyl-3,7, 11 ,17- tetraazabicyclo( 11.3 .1 )-heptadeca-1 ( 17),2, 11 ,13, 15-pentaene, was chosen as the complex in this study based on previous studies that showed it to be the most active complex among a series of square planar nickel complexes in promoting DNA oxidation. This complex was synthesized and its structure was proven by electrospray mass spectroscopy, H-NMR, and elemental analysis. The H-NMR data also demonstrated that this complex has two vacant coordination sites in the distorted octahedral form in aqueous solution. Histone and bovine serum albumin which are typical proteins in eukaryote animals were chosen as the target materials when I studied whether this nickel complex could bind to proteins in the body. Nickel complex was labeled with Ni63 during the dialysis, and counted by a liquid scintillation counter.

No description available.

Complexes of the general formula M(X-SALDAPE) and M(X-SALDAPS) formed by the reaction of substituted salicylaldehydes and bis(3,3'-aminopropyl)ether or bis(3,3'-aminopropyl)sulfide with nickel(II) and cobalt(II) have been isolated. The complexes have been characterized by elemental analysis, mass spectra, infrared spectra, magnetic susceptibility measurements, and ultraviolet-visible-near infrared spectra. In the solid state the nickel(II) complexes, Ni(X-SALDAPE) and Ni(X-SALDAPS), where X = H, 5-Br, 3-(CH₃)₂CH, or 3-CH₃O, are speculated as pseudo-square planar or weak low-spin five-coordinate structures. The complexes exhibit anomalous magnetic behavior explained in terms of a spin state isomerism between singlet and triplet spin states. In a non-coordinating solvent, the nickel complexes are pseudo-square planar losing all five-coordinate structural features due to salvation. When dissolved in a coordinating solvent, the complexes are high-spin pseudo-octahedral. The cobalt(II) complexes, Co(H-SALDAPE) and Co(X-SALDAPS) where X = H, or 3-(CH₃)₂CH, were found to be high-spin pseudo-tetrahedral in the solid state with magnetic moments of approximately 3.4 B.M. The olive green nickel complexes are stable to air and moisture. The brownish cobalt complexes are stable as dry solids, but very easily oxidized when wet. / Master of Science

Thesis (Ph. D.)--University of Texas at Austin, 2007. / Vita. Includes bibliographical references.

Tez (Doktora) - Süleyman Demirel Üniversitesi, Fen Bilimleri Enstitüsü, Kimya Anabilim Dalı, 2007. / Bibliyografya var.

Thesis (Ph. D.)--State University of New York at Binghamton, Department of Chemistry, 2008. / Includes bibliographical references.

Ph.D. / This thesis deals with the synthesis of nitrogen-donor compounds and their reaction with metal ions. The first type of nitrogen-donor compounds are the unconjugated diimines (N,N´-bis(diphenylmethylene)ethylenediamine (L1) and (N,N´-bis(diphenylmethylene)propylenediamine (L2). Compounds L1 and L2 were reacted with [NiBr2(DME)] or [NiCl2·6H2O] to form complexes (2.1a), (2.2a), (2.3a) and (2.4a). These nickel complexes were characterized by IR spectroscopy, elemental analysis and mass spectrometry. When the complexes were left in chloroform for prolonged periods, hydrolysis of the diimine ligand took place, leading to the formation of nickel complexes 2.1b, 2.2b, 2.3b and 2.4b. The identity of the hydrolysed nickel complexes 2.1b and 2.2b was confirmed by single crystal X-ray crystallography. Complex 2.1b crystallised in the P21/n space group, whilst 2.2b crystallised in the P-1 space group. Compounds L1 and L2 were also reacted with [PdClMe(MeCN)2] to form the palladium complexes (3.1) and (3.2). The palladium complexes were characterized by NMR spectroscopy, elemental analysis and single crystal X-ray crystallography. Attempts to recrystallize 3.1 from a dichloromethane solution led to the formation of 3.1a. Both complexes 3.1a and 3.2 crystallised in the P21/n space group. Complexes 3.1 and 3.2 were tested as catalysts for the Heck coupling reaction of iodobenzene with methyl acrylate or butyl acrylate at 80 C. The products from the coupling reactions were characterized by GC and NMR spectroscopy. These complexes were found to be highly active with 100% conversions observed in some instances. The second type of ligands that were prepared are the benzoylpyrazolyl compounds, (3,5-dimethylpyrazol-1-yl)phenylmethanone (C1), (3,5-ditertiarybutylpyrazol-1-yl)phenylmethanone (C2), (3,5-dimethylpyrazol-1-yl)-o-toluoylmethanone (C3), (3,5-ditertiarybutylpyrazol-1-yl)-o-toluoylmethanone (C4), (2-chlorophenyl)-(3,5-dimethylpyrazol-1-yl)methanone (C5), (2-chlorophenyl)-(3,5-ditertiarybutylpyrazol-1-yl)methanone (C6), (2-flourophenyl)-(3,5-dimethylpyrazol-1-yl)methanone (C7), (2-flourophenyl)-(3,5-ditertiarybutylpyrazol-1-yl)methanone (C8). These compounds were fully characterized using NMR spectroscopy, IR spectroscopy and elemental analysis. Compounds C1, C3, C5 and C7 were reacted with [NiBr2(DME)] to form nickel complexes (4.31-4.34). These nickel complexes were found to be insoluble in all common organic solvents and hence were characterized only by IR spectroscopy and elemental analysis. Compounds C1-C8 were also reacted with [PdCl2(MeCN)2] to form palladium complexes (4.35-4.42). Complexes 4.35-4.42 were characterized using NMR spectroscopy, IR spectroscopy, elemental analysis and in selected cases single crystal X-ray crystallography. Complex 4.39 crystallised in the C2/n space group and complex 4.42 crystallised in the P21/n space group. Attempts to recrystallize 4.37a led to the formation of 4.37b, which contains both 3,5-dimethylpyrazol-1-yl)-o-toluoylmethanone and 3,5-dimethylpyrazole as ligands. Complex 4.37b was confirmed by NMR spectroscopy and single crystal X-ray crystallography. Complex 4.37b crystallised in the Pbca space group. The formation of 4.37b is attributed to hydrolysis of 3,5-dimethylpyrazol-1-yl)-o-toluoylmethanone ligand in 4.37a due to the presence of adventitious water in the solvent. The palladium complexes (4.35-4.42) were tested as catalysts for the Heck coupling reaction of iodobenzene with butyl acrylate and also for the Suzuki coupling reaction of iodobenzene with phenylboronic acid or 4-chlorophenylboronic acid. In these reactions, complexes 4.35-4.42 were found to be highly active at 120 C. The pyrazolyl nickel and palladium complexes were further tested as catalysts in ethylene oligomerization reactions using EtAlCl2 as the co-catalyst. The nickel complexes were found to be the most active reaching TONs of 10.8105 g mol-1 h-1. The palladium analogues only gave TONs of up to 3.9105 g mol-1 h-1. The oligomers were characterized by GC and NMR spectroscopy and were found to be in the C10-C16 range, with C16 the most abundant olefin.