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Dermot O'Hare

Publications and source records attributed to Dermot O'Hare.

13 recordsLinked to original sources
PubMed2003

Controlled structural variations in templated uranium sulfates.

A series of experiments in the UO(2)(CH(3)CO(2))(2).2H(2)O/H(2)SO(4)/1-(2-aminoethyl)piperazine/H(2)O system were conducted to determine the effects of variation in initial reactant concentrations on the reaction products. Several reaction gels were produced, in which the composition varied from 16:80:4:500 UO(2)(CH(3)CO(2))(2).2H(2)O/H(2)SO(4)/1-(2-aminoethyl)piperazine/H(2)O to 4:92:4:500 UO(2)(CH(3)CO(2))(2).2H(2)O/H(2)SO(4)/1-(2-aminoethyl)piperazine/H(2)O. Single crystals of two new organically templated uranium sulfates, [N(3)C(6)H(18)](2)[(UO(2))(5)(H(2)O)(SO(4))(8)].5H(2)O and [N(3)C(6)H(18)][(UO(2))(2)(H(2)O)(SO(4))(3)(HSO(4))].4.5H(2)O, were isolated. Both compounds exhibit structures in which the inorganic frameworks are two-dimensional and the protonated amines reside between layers, participating in extensive hydrogen bonding. The composition and structure of each compound is dependent on the nature of the starting concentrations. Crystal data: for [N(3)C(6)H(18)](2)[(UO(2))(5)(H(2)O)(SO(4))(8)].5H(2)O, monoclinic, space group P2(1)/n (No. 14), a = 21.5597(3) A, b = 10.2901(2) A, c = 22.8403(3) A, beta = 96.7436(7) degrees, and Z = 4; for [N(3)C(6)H(18)][(UO(2))(2)(H(2)O)(SO(4))(3)(HSO(4))].4.5H(2)O, monoclinic, space group P2(1)/a (No. 14), a = 15.7673(4) A, b = 10.5813(3) A, c = 16.7710(5) A, beta = 99.9216(9) degrees, and Z = 4.

Journal Article↗
PubMed2003

Electronic structures of mixed-sandwich complexes of cyclopentadienyl and Hydrotris(pyrazolyl)borate ligands with 3d transition metals.

The electronic and magnetic properties of a series of mixed-sandwich complexes MCp(R)Tp (Cp(R) = Cp or Cp; Tp = hydrotris(pyrazolyl)borate; M = V, Cr, Fe, Co or Ni) have been studied and compared to their homoleptic analogues, MCp(R)(2) and MTp(2). Solid-state magnetic susceptibility measurements and EPR spectroscopic data indicate that complexes with d(3), d(6), and d(8) configurations are similar electronically to their metallocene analogues, except for FeCpTp, which displays a spin equilibrium (S = 0 if S = 2) in solution which was investigated by variable- temperature NMR spectroscopy. The d(2) complex [VCpTp](+) displays magnetic behavior consistent with an orbitally nondegenerate ground state. The d(4) species CrCpTp has a high-spin (S = 2) ground state. The d(7) species CoCpTp is high spin (S = 3/2) whereas its Cp analogue and [NiCpTp](+) are both low-spin (S = 1/2) species. The optical spectra of the d(3), d(6), and d(8) complexes were assigned in a fashion similar to the analogous metallocenes and ligand-field parameters (delta(1) = delta-sigma gap, delta(2) = sigma-pi gap for d-orbitals in axial symmetry) calculated. The analysis shows that for 15-electron species the total ligand-field splitting, delta(TOT), is larger than for their metallocene analogues, whereas for the 18-electron case Delta(TOT) is smaller and for 20-electron systems delta(TOT) is approximately the same. In all cases delta(2) is substantially reduced compared to the metallocenes, and in the majority of cases delta(1) is markedly larger. DFT calculations were performed to investigate further the nature of the ligand environment on the frontier orbitals in these complexes. Orbital energies and compositions were calculated and compared for a series of homoleptic and mixed-sandwich complexes of Ni(II) and across the 1st transition series for MCp(R)Tp species. The ability of Tp (vs Cp) to act as a delta-donor (with respect to the principal molecular axis) imparts significant ligand antibonding character to the delta-orbitals and results in decreased epsilon(pi)-epsilon(delta) values compared to the metallocenes and an increased tendency toward high-spin complexes in the mixed-sandwich complexes. Structure calculations were performed for CrCpTp, [VCpTp](+), and CoCpTp which show substantial distortions from ideal axial symmetry in their crystal structures. The origins of these distortions were confirmed to arise from unequal occupancy of near-degenerate delta- and pi-levels.

Journal Article↗
PubMed2003

Solid-state chelation of metal ions by ethylenediaminetetraacetate intercalated in a layered double hydroxide.

The solid-state chelation of transition metal ions (Co(2+), Ni(2+), and Cu(2+)) from aqueous solutions into the lithium aluminum layered double hydroxide ([LiAl(2)(OH)(6)]Cl x 0.5H(2)O or LDH) which has been pre-intercalated with EDTA (ethylenediaminetetraacetate) ligand has been investigated. The intercalated metal cations form [M(edta)](2)(-) complexes between the LDH layers as indicated by elemental analysis, powder X-ray diffraction, and IR and UV-vis spectroscopies. If metal chloride or nitrate salts are used in the reaction with the LDH then co-intercalation of either the Cl(-) or NO(3)(-) anions is observed. In the case of metal acetate salts the cations intercalate without the accompanying anion. This can be explained by the different intercalation selectivity of the anions in relation to the LDH. In the latter case the introduction of the positive charge into LDH structure was compensated for by the release from the solid of the equivalent quantity of lithium and hydrogen cations. Time-resolved in-situ X-ray diffraction measurements have revealed that the chelation/intercalation reactions proceed very quickly. The rate of the reaction found for nickel acetate depends on concentration as approximately k[Ni(Ac)(2)](3).

Journal Article↗
PubMed2003

Recent results from the in situ study of hydrothermal crystallisations using time-resolved X-ray and neutron diffraction methods.

We present new time-resolved powder diffraction data measured in situ during the hydrothermal crystallisation of two families of crystalline inorganic materials. In the first study, we have used time-resolved energy-dispersive X-ray diffraction (EDXRD) to follow the formation of zeolitic zinc phosphates from amine phosphates and zinc oxide in acidic solutions at 60-150 degrees C. The advantage of this method is the ability to penetrate a laboratory-sized reaction vessel and to measure data in short (< 1 min) time intervals. Integration of the Bragg peak intensities during the crystallisation of the product allows accurate crystallisation curves to be produced. In addition, in a number of cases, we observe the formation of transient crystalline intermediate phases which can be identified by use of a new three-element detector that allows a large amount of diffraction data to be measured during the experiment. We are thus able to show that three-dimensional zinc phosphate architectures often form via low-dimensional chain and layered phases, which is consistent with a recent aufbau model proposed for their formation. In the second study, we focus on the hydrothermal formation of ferroelectric barium titanate from TiO2 and barium salts in alkaline solution using time-resolved neutron diffraction. Although the time resolution of the neutron diffraction experiment is lower than the EDXRD experiment (data are measured in intervals of 5 min), we are able to penetrate reaction mixtures that are highly absorbing towards X-rays, and thus can measure data in a large volume reaction cell. Neutron diffraction data were collected on one of the highest-flux/highest detector-coverage diffractometers currently available; the GEM diffractometer at ISIS, UK. These experiments reveal that BaTiO3 crystallises after a large amount of TiO2 has been consumed; this implies that a dissolution crystallisation mechanism predominates. Additional mechanistic information is inferred by the observation of transient crystalline phases under certain reaction conditions.

Journal Article↗
PubMed2002

Pentalene complexes of group 7 metal carbonyls: an organometallic mixed-valence system with very large metal-metal electronic coupling.

The bimetallic complexes [M(CO)(3)](2)(mu:eta(5):eta(5)-Pn) (Pn = pentalene, C(8)H(6); M = Mn, Re) have been synthesized and characterized crystallographically; the Mn compound was isolated as solely the anti-isomer, while the Re analogue was formed as a mixture of anti- and syn-isomers. [Mn(CO)(3)](2)(mu:eta(5):eta(5)-Pn) may be reduced chemically to its mono- and dianions; the mixed-valence Mn(I)/Mn(0) monoanion is shown by ESR, vibrational, and electronic spectroscopies to be a Robin-Day class III system with an exceptionally large electronic coupling between the metal centers.

Journal Article↗
PubMed2002

Two chain gallium fluorodiphosphates: synthesis, structure solution, and their transient presence during the hydrothermal crystallisation of a microporous gallium fluorophosphate.

Two novel gallium fluorodiphosphates have been isolated and their structures solved ab initio from powder X-ray diffraction data; the materials readily interconvert under hydrothermal conditions, and are metastable with respect to an open-framework zeolitic gallium fluorophosphate, during the synthesis of which they are present as transient intermediates.

Crystallography↗
PubMed2002

CrCpTp: a high-spin Cr(II) sandwich complex with a large structural distortion.

CrCpTp was synthesized from the reaction of [CrCpCl](2) and KTp. Magnetic measurements indicate it to have a high-spin (S = 2) electronic configuration from 5 to 300 K. A single-crystal X-ray study reveals bond lengths typical for a high-spin configuration and a pronounced Jahn-Teller distortion. The nature of this distortion was probed by DFT calculations and the variation in bond lengths successfully reproduced. The metal-based HOMO is significantly antibonding with respect to a single pyrazolyl ring only.

Journal Article↗
PubMed2000

Crystallization of a Large-Pore Three-Dimensional Gallium Fluorophosphate under Mild Conditions This work was supported by EPSRC and the Novartis Trust Fund. The EPSRC provided access to Daresbury Laboratory. We are grateful to L. M. D. Cranswick of Daresbury Laboratory for valuable discussions, Dr. S. O'Leary (Oxford) for performing the thermogravimetric analysis (TGA) measurements, and Professor K. Kuroda (Waseda University) for performing the gas adsorption measurements. The authors acknowledge the EPSRC-funded Collaborative Computational Project Number 14 (http://www.ccp14.ac.uk) for software resources applied in data analysis.

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Journal Article↗