Atomistic Modeling of Silica Based Sol-Gel Processes

Density Functional Theory is used to study water, methanol, ethanol, TMOS, and TEOS molecules and the most important silica clusters participating in sol-gel processes. Calculated bond lengths, bond angles and electric dipole moments compare well with experimental data. The energy of these molecules is reported and used to discuss the energetics of the hydrolysis and condensation reactions. Molecular Dynamics is employed to simulate liquid water, methanol, ethanol, TMOS, TEOS and experimental sol-gel solutions. Calculated densities and enthalpies of vaporisation compare well with experimental data. Preliminary results are presented for MD simulations of sol-gel solutions.     

Determination of trace impurities in boron nitride by graphite furnace atomic absorption spectrometry and electrothermal vaporization inductively coupled plasma optical emission spectrometry using solid sampling

Two digestion-free methods for trace analysis of boron nitride based on graphite furnace atomic absorption spectrometry (GFAAS) and electrothermal vaporization inductively coupled plasma spectrometry optical emission (ETV-ICP-OES) using direct solid sampling have been developed and applied to the determination of Al, Ca, Cr, Cu, Fe, Mg, Mn, Si, Ti and Zr in four boron nitride materials in concentration intervals of 1–23, 54–735, 0.05–21, 0.005–1.3, 1.6–112, 4.5–20, 0.03–1.8, 6–46, 38–170 and 0.4–2.3 μg g^− 1, respectively. At optimized experimental conditions, with both methods, effective in-situ analyte/matrix separation was achieved and calibration could be performed using calibration curves measured with aqueous standard solutions. In solid sampling GFAAS, before sampling, the platform was covered with graphite powder and, for determination of Si, also the Pd/Mg(NO₃)₂ modifier was used. In the determination of all analyte elements by solid sampling ETV-ICP-OES, Freon R12 was added to argon carrier gas. For solid sampling GFAAS and ETV-ICP-OES, the achievable limits of detection were within 5 (Cu)–130 (Si) ng g^− 1 and 8 (Cu)–200 (Si) ng g^− 1, respectively. The results obtained by these two methods for four boron nitride materials of different purity grades are compared each with the other and with those obtained in analysis of digests by ICP-OES. The performance of the two solid sampling methods is compared and discussed.     

Electrochemical behaviour of some polyoxo clusters

We describe the redox behaviour in non-aqueous solvents of some cyclopentadienyl(oxo)titanium derivatives. The derivative [Ti₄{η⁵-C₅H₄(SiMe₃)}₄(μ-O)₆] shows an electrochemically and chemically reversible le reduction process, followed by a multi-electron, chemically complicated reduction at a fairly cathodic potential. On the basis of the overall electrochemical features and the comparison with the redox behaviour of the quasi-planar compound [[Ti{η⁵-C₅H₄(SiMe₃)}Cl(μ-O)]₄] we propose an EECCEE mechanism for the first derivative, where the second electron-transfer induces a cascade of chemical reactions giving rise to irreversible cluster breakdown. The electrochemically induced fragmentation can be viewed as a retrosynthetic pathway. The heterometallic derivative [{Ti(η⁵-C₅H₄Me)₂(μ₂-MoO₄)₂}₂] shows two consecutive reduction processes; the first is chemically reversible, and the second quasi-reversible. The molybdate bridges apparently increase the stability of the electrogenerated anions. However none of these poly-oxo clusters can be considered as good models of electron ‘sinks’.     

The electronic structure of small sodium clusters

Ab initio molecular orbital calculations using the STO3-21G basis set has been carried out for the cluster series Na _n ⁺ , Na _n , and Na _n ^– (wheren=2–7). The basis set is shown to be reliable compared with more extensive basis sets at the Hartree-Fock level. Thirty-one optimized structures are reported and discussed, many of which (especially for the anions) have not been considered. The STO3-21G//STO3-21G calculations suggest that for most of the species the optimum geometries are planar. In particular, the optimized structures for the anionic species should provide a starting point for more sophisticated configuration interaction calculations.     

Some thermodynamic aspects of nitrides in materials science

The energies of combustion in fluorine of gallium nitride and indium nitride in wurzite crystalline structure have been measured in a two-compartment calorimetric bomb, and new standard molar enthalpies of formation have been calculated: Δ_fH_m⁰(GaN(cr) 298.15 K)= –(163.7±4.2) kJ mol^–1 and Δ_fH_m⁰(InN(cr) 298.15 K)= –(146.5±4.6) kJ mol^–1 . Comparison with the recommended values of the Δ_fH_m⁰ nitrides from the literature is also presented.     

The oxidative addition of diphenylphosphine and monophenylphosphine to the electron-rich rhenium-rhenium triple bond. The isolation and characterization of compounds that contain the four-center Re(μ-X)(μ-PR2)Re cluster (X=halide)

Diphenylphosphine oxidatively adds to the ReRe bonds of Re₂ X ₄(-dppm)₂ (X=Cl or Br; dppm=Ph₂PCH₂PPh₂) and Re₂Cl₄(-dpam)₂ (dpam=Ph₂AsCH₂AsPh₂) to afford the dirhenium(III) complexes Re₂(-X)(-PPh₂)HX ₃(-LL)₂. The dppm complexes have also been prepared from the reactions of Re₂(-O₂CCH₃)X ₄(-dppm)₂ with Ph₂PH, and a similar strategy has been used to prepare Re₂(-Cl)(-PPh₂)HCl₃(-dmpm)₂ (dmpm=Me₂PCH₂PMe₂) from Re₂(-O₂CCH₃)Cl₄(dmpm)₂. Phenylphosphine likewise reacts with Re₂ X ₄(-dppm)₂ to give Re₂(-X)(-PHPh)HX ₃(-dppm)₂. An X-ray crystal structure determination on Re₂(-Cl)(-PPh₂)HCl₃(-dppm)₂ confirms its edge-shared bioctahedral structure. This complex crystallizes in the space group (No. 148) witha=21.699(3) Å, =84.50(4)°,V=10084(5) ų, andZ=6. The structure was refined toR=0.049 (R _w 0.069) for 5770 data withI>3.0(I). The Re-Re distance is 2.5918(7) Å. Oxidation of the bromide complex Re₂(-Br)(-PPh₂)HBr₃(-dppm)₂ with NOPF₆ produces the unusual dirhenium(III, II) cation [Re₂(-H)(-Br)[P(O)Ph₂]Br₂(NO)(-dppm)₂]⁺ which has been structurally characterized as its perrhenate salt, [Re₂(-H)(-Br)[P(O)Ph₂]Br₂(NO)(-dppm)₂]ReO₄ · 2CH₂Cl₂. This complex crystallizes in the space group (No. 2) witha=14.187(7) Å,b=16.419(5) Å,c=16.729(5) Å, =98.76(2)°, =110.11(3)°, =104.66(3)°,V=3414(6) ų,Z=2. The structure was refined toR=0.040 (R _w =0.051) for 5736 data withI>3.0(I). The presence of a phosphorus-bound [P(O)Ph₂]^– ligand, a linear nitrosyl and a bridging hydrido ligand has been confirmed. The Re-Re distance is 2.6273(8) Å.     

Free electron model in cluster structure theory. Electronic structures of [Mo6S8(CN)6]6?, [Mo6Se8(CN)6]6?, [Re6S8(CN)6]4?, and Rh6(CO)16 clusters

The results of quantum chemical calculations of the electronic structure and geometry of octahedral clusters [Mo₆S₈(CN)₆]⁶⁻, [Mo₆Se₈(CN)₆]⁶⁻, [Re₆S₈(CN)₆]⁴⁻, and Rh₆(CO)₁₆ by the ab initio SCF (RHF) and DFT (B3LYP) methods with various basis sets are presented. The electronic states of the clusters under study in ideal spherically symmetric potential were classified in the orbital quantum number l (1s, 1p, 1d, 1f, 1g, 1h, 1i), l = 0–6. In real crystal field with O_h symmetry these states are split. The calculated new electronic states were matched to the irreducible representations of the point symmetry group O_h. The polarizabilities of the compounds considered are 55–65 ų. A new model for the electronic structure of octahedral clusters containing M₆ groups was proposed. The model is based on the idea of free electrons moving in spherically symmetric potential field. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2617–2624, December, 2005.     

Ionization energy reductions in small 2,5-dihydroxybenzoic acid-proline clusters

The photoionization of (pro)(n)DHB (pro = proline, DHB = 2,5-dihydroxybenzoic acid, n = 0, 1, 2 or 4) clusters was studied both experimentally and computationally. Experimentally the (pro)(n)DHB clusters are generated in the gas phase by laser desorption and supersonic jet entrainment. The photoionization thresholds are then determined by the mass-selective measurement of both one- and two-color photoionization efficiency curves. These experiments demonstrate that the ionization energies (IEs) of the (pro)(n)DHB clusters are substantially reduced in comparison with the IE of free DHB. Computational studies of the (pro)(n)DHB clusters provide insights into the mechanism of IE reduction. For the (pro)DHB system the IE reduction results from spin delocalization in the ion state of the cluster. In contrast, for the (pro)(2)DHB and (pro)(4)DHB clusters the IE reduction results from an inductive delocalization of electron density from pro to DHB in the ground state of the cluster. This latter effect, which is a result of the specific hydrogen-bonding interactions occurring in the mixed clusters, leads to IE reductions of >1 eV. Finally, determination of the energetics of the (pro)(2)DHB radical cation demonstrate that the DHB-to-proline proton transfer reaction is a barrierless, exoergic process in the ion state and that energetic demands for cluster dissociation to protonated (pro)(2) plus a deprotonated DHB radical are substantially lower than those for cluster dissociation to (pro)(2) plus DHB(+*). Cumulatively, these studies provide new energetic and mechanistic insights into both primary and secondary MALDI ionization processes.     

Synthesis, structures and reactivity of triosmium clusters containing terminal pyrazines, bridging hydroxy and methoxycarbonyl ligands

Four triosmium carbonyl clusters bearing terminal pyrazines, bridging hydroxy and methoxycarbonyl ligands of general formula [Os₃(CO)₉(μ-OH)(μ-OMeCO)L] (1, L = pyrazine; 2, L = 2-methylpyrazine; 3, L = 2,3-dimethylpyrazine; 4, L = 2,3,5-trimethylpyrazine) were synthesized by the reactions of [Os₃(CO)₁₂] with the corresponding pyrazine derivatives and water in the presence of a methanolic solution of Me₃NO in moderate yields. Compounds [Os₃(CO)₉(μ-OH)(μ-OMeCO)L] react with a series of two electron donor ligands, L′ at ambient temperature to give [Os₃(CO)₉(μ-OH)(μ-OMeCO)L′] (5, L′ = PPh₃; 6, L′ = P(OMe)₃; 7, L′ = ^tBuNC; 8, L′ = C₅H₅N) in good yields by the displacement of the pyrazine ligands. This implies that the pyrazine ligands in 1–4 are relatively labile. Compounds 2, 3, 4, and 8 were characterized by single crystal X-ray diffraction analyses. All the four compounds possess two metal–metal bonds and a non-bonded separation of two osmium atoms defined by Os(1)Os(3), which are simultaneously bridged by OH and MeOCO ligands and a heterocyclic ligand is terminally coordinated to one of the two non-bonded osmium atoms.