Monica Vasiliu

Regeneration of Ammonia Borane Spent Fuel by Direct Reaction with Hydrazine and Liquid Ammonia

A method to regenerate lightweight, hydrogen-rich ammonia borane improves its prospects as a vehicular fuel source. Ammonia borane (H3N-BH3, AB) is a lightweight material containing a high density of hydrogen (H2) that can be readily liberated for use in fuel cell–powered applications. However, in the absence of a straightforward, efficient method for regenerating AB from dehydrogenated polymeric spent fuel, its full potential as a viable H2 storage material will not be realized. We demonstrate that the spent fuel type derived from the removal of greater than two equivalents of H2 per molecule of AB (i.e., polyborazylene, PB) can be converted back to AB nearly quantitatively by 24-hour treatment with hydrazine (N2H4) in liquid ammonia (NH3) at 40°C in a sealed pressure vessel.

BN-substituted diphenylacetylene: a basic model for conjugated π-systems containing the BN bond pair

We report the synthesis, structural characterization, and optoelectronic properties of BN-Tolan 1 and Bis-BN-Tolan 2, one of the simplest conjugated systems containing the BN bond pair. BN-tolans 1 and 2 display absorption and emission properties that are distinct from their carbonaceous analogue, tolan. In addition, Bis-BN-Tolan 2 exhibits unique N–H⋯π(C≡C) hydrogen bonding in the solid state.

Emergence of californium as the second transitional element in the actinide series

A break in periodicity occurs in the actinide series between plutonium and americium as the result of the localization of 5f electrons. The subsequent chemistry of later actinides is thought to closely parallel lanthanides in that bonding is expected to be ionic and complexation should not substantially alter the electronic structure of the metal ions. Here we demonstrate that ligation of californium(III) by a pyridine derivative results in significant deviations in the properties of the resultant complex with respect to that predicted for the free ion. We expand on this by characterizing the americium and curium analogues for comparison, and show that these pronounced effects result from a second transition in periodicity in the actinide series that occurs, in part, because of the stabilization of the divalent oxidation state. The metastability of californium(II) is responsible for many of the unusual properties of californium including the green photoluminescence.

Spectroscopic and energetic properties of thorium(IV) molecular clusters with a hexanuclear core.

The spectral and energetic properties of three polynuclear thorium(IV) molecular complexes Th(6)(OH)(4)O(4)(H(2)O)(6)(HCOO)(12)·nH(2)O (1), Th(6)(OH)(4)O(4)(H(2)O)(6)(CH(3)COO)(12)·nH(2)O (2), and Th(6)(OH)(4)O(4)(H(2)O)(6)(ClCH(2)COO)(12)·4H(2)O (3) have been studied. Each complex has a hexanuclear core with six 9-coordinate Th(IV) cations bridged by four μ(3)-hydroxo and four μ(3)-oxo groups. The +12 core is stabilized by twelve bridging carboxylate functionalized organic acid (formate, acetate, and chloroacetate) units. The calculated (1)H NMR chemical shifts for the four μ(3)-hydroxo, water, and formate protons are reported and compared to the experimental values. The vibrational frequencies were calculated to aid in the assignment of the observed Raman bands. The Mulliken and NBO (natural bond orbital) charges are calculated for the Th clusters. The Th atoms are positive and the bridging O and O(H) are negative. The analysis of the calculated highest-occupied and lowest-unoccupied molecular orbitals (HOMO and LUMO) is reported. The average water complexation energies, the gas phase, the aqueous and dimethylsulfoxide (DMSO) acidities were predicted, and the Th clusters are found to be mild to strong acids in gas phase yet they behave as weak acids in solution.

Late-Stage Functionalization of 1,2-Dihydro-1,2-azaborines via Regioselective Iridium-Catalyzed C–H Borylation: The Development of a New N,N-Bidentate Ligand Scaffold

The first general late-stage functionalization of monocyclic 1,2-azaborines at the C(6) position is described. Ir-catalyzed C-H borylation occurs regioselectively at the C(6) position of B-substituted 1,2-azaborines and is compatible with a range of substitution patterns at boron (e.g., hydride, alkoxide, alkyl, and aryl substituents). Subsequent Suzuki cross coupling with aryl- and heteroaryl bromides furnishes 1,2-azaborine-based biaryl compounds including 6-[pyrid-2-yl]-1,2-azaborines that represent novel κ(2)-N,N-bidentate ligands. The 6-[pyrid-2-yl]-B-Me-1,2-azaborine ligand has been demonstrated to form an emissive coordination complex with dimesitylboron that exhibits bathochromically shifted absorption and emission maxima and a higher photoluminescence quantum yield compared to its carbonaceous analogue.

Structures and heats of formation of simple alkaline earth metal compounds: fluorides, chlorides, oxides, and hydroxides for Be, Mg, and Ca.

Geometry parameters, frequencies, heats of formation, and bond dissociation energies are predicted for the simple alkaline earth (Be, Mg and Ca) fluorides, chlorides, oxides, and hydroxides at the coupled cluster theory [CCSD(T)] level including core-valence correlation with the aug-cc-pwCVnZ basis sets up to n = 5 in some cases. Additional corrections (scalar relativistic effects, vibrational zero-point energies, and atomic spin-orbit effects) were necessary to accurately calculate the total atomization energies and heats of formation. The calculated geometry parameters, frequencies, heats of formation, and bond dissociation energies are compared with the available experimental data. For a number of these alkaline earth compounds, the experimental geometries and energies are not reliable. MgF(2) and BeF(2) are predicted to be linear and CaF(2) is predicted to be bent. BeOH is predicted to be bent, whereas MgOH and CaOH are linear. The OBeO angle in Be(OH)(2) is not linear, and the molecule has C(2) symmetry. The heat of formation at 298 K for MgO is calculated to be 32.3 kcal/mol, and the bond dissociation energy at 0 K is predicted to be 61.5 kcal/mol.

Structures and heats of formation of simple alkali metal compounds: hydrides, chlorides, fluorides, hydroxides, and oxides for Li, Na, and K.

Geometry parameters, frequencies, heats of formation, and bond dissociation energies are predicted for simple alkali metal compounds (hydrides, chlorides, fluorides, hydroxides and oxides) of Li, Na, and K from coupled cluster theory [CCSD(T)] calculations including core-valence correlation with the aug-cc-pwCVnZ basis set (n = D, T, Q, and 5). To accurately calculate the heats of formation, the following additional correction were included: scalar relativistic effects, atomic spin-orbit effects, and vibrational zero-point energies. For calibration purposes, the properties of some of the lithium compounds were predicted with iterative triple and quadruple excitations via CCSDT and CCSDTQ. The calculated geometry parameters, frequencies, heats of formation, and bond dissociation energies were compared with all available experimental measurements and are in excellent agreement with high-quality experimental data. High-level calculations are required to correctly predict that K(2)O is linear and that the ground state of KO is (2)Sigma(+), not (2)Pi, as in LiO and NaO. This reliable and consistent set of calculated thermodynamic data is appropriate for use in combustion and atmospheric simulations.

Thermochemistry of Lewis Adducts of BH3 and Nucleophilic Substitution of Triethylamine on NH3BH3 in Tetrahydrofuran

The thermochemistry of the formation of Lewis base adducts of BH(3) in tetrahydrofuran (THF) solution and the gas phase and the kinetics of substitution on ammonia borane by triethylamine are reported. The dative bond energy of Lewis adducts were predicted using density functional theory at the B3LYP/DZVP2 and B3LYP/6-311+G** levels and correlated ab initio molecular orbital theories, including MP2, G3(MP2), and G3(MP2)B3LYP, and compared with available experimental data and accurate CCSD(T)/CBS theory results. The analysis showed that the G3 methods using either the MP2 or the B3LYP geometries reproduce the benchmark results usually to within ~1 kcal/mol. Energies calculated at the MP2/aug-cc-pVTZ level for geometries optimized at the B3LYP/DZVP2 or B3LYP/6-311+G** levels give dative bond energies 2-4 kcal/mol larger than benchmark values. The enthalpies for forming adducts in THF were determined by calorimetry and compared with the calculated energies for the gas phase reaction: THFBH(3) + L → LBH(3) + THF. The formation of NH(3)BH(3) in THF was observed to yield significantly more heat than gas phase dative bond energies predict, consistent with strong solvation of NH(3)BH(3). Substitution of NEt(3) on NH(3)BH(3) is an equilibrium process in THF solution (K ≈ 0.2 at 25 °C). The reaction obeys a reversible bimolecular kinetic rate law with the Arrhenius parameters: log A = 14.7 ± 1.1 and E(a) = 28.1 ± 1.5 kcal/mol. Simulation of the mechanism using the SM8 continuum solvation model shows the reaction most likely proceeds primarily by a classical S(N)2 mechanism.

Gas Phase Properties of MX2 and MX4 (X = F, Cl) for M = Group 4, Group 14, Cerium, and Thorium.

Structures, vibrational frequencies, and heats of formation were predicted for MX4 and both singlet and triplet states of MX2 (M = group 4, group 14, Ce, and Th; X = F and Cl) using the Feller-Peterson-Dixon composite electronic structure approach based on coupled cluster CCSD(T) calculations extrapolated to the complete basis set limit with additional corrections including spin orbit effects. The spin-orbit corrections are not large but need to be included for chemical accuracy of ±1 kcal/mol. The singlet-triplet splittings were calculated for the dihalides and all compounds have singlet ground states except for the dihalides of Ti, Zr, and Ce which have triplet ground states. The calculated heats of formation are in good agreement with the available experimental data. Our predictions suggest that the experimental heats of formation need to be revised for a number of tetrahalides: TiF4, HfF4, PbF4, PbCl4, and ThCl4 as well as a number of dihalides: GeF2, SnF2, PbF2, TiF2, and TiCl2. The calculated heats of formation were used to predict various thermodynamic properties including average M-F and M-Cl bond dissociation energies and the reaction energies for MX2 + X2 → MX4. Edge inversion barriers were predicted. The calculated edge inversion barriers for the tetrafluorides show that the barriers for the group 14 tetrafluorides decrease with increasing atomic number, the group 4 barriers are ∼50 kcal/mol and CeF4 and ThF4 have inversion barriers of ∼25 kcal/mol.

A Modular Synthetic Approach to Monocyclic 1,4-Azaborines.

A simple and general method for the synthesis of a wide range of monocyclic 1,4-azaborines, including the first examples containing B heteroatoms is described. Post-heterocycle-formation olefin isomerization was employed as a key strategy. This new synthetic method provides fundamental insight into the resonance stabilization and photophysical properties of 1,4-azaborines.