Ammonia borane (H(3)N-BH(3), AB) is a lightweight material containing a high density of hydrogen (H(2)) 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 H(2) storage material will not be realized. We demonstrate that the spent fuel type derived from the removal of greater than two equivalents of H(2) per molecule of AB (i.e., polyborazylene, PB) can be converted back to AB nearly quantitatively by 24-hour treatment with hydrazine (N(2)H(4)) in liquid ammonia (NH(3)) at 40°C in a sealed pressure vessel.

Three polynuclear thorium(IV) molecular complexes have been synthesized under ambient conditions from reactions of an amorphous Th precipitate, obtained via hydrolysis, with carboxylate functionalized ligands. The structures of Th(6)(OH)(4)O(4)(H(2)O)(6)(HCO(2))(12)·nH(2)O (1), Th(6)(OH)(4)O(4)(H(2)O)(6)(CH(3)CO(2))(12)·nH(2)O (2), Th(6)(OH)(4)O(4)(H(2)O)(6)(ClCH(2)CO(2))(12)·4H(2)O (3) each consist of a hexanuclear Th core wherein six 9-coordinate Th(IV) cations are bridged by four μ(3)-hydroxo and four μ(3)-oxo groups. Each Th(IV) center is additionally coordinated to one bound "apical" water molecule and four oxygen atoms from bridging carboxylate functionalized organic acid units. "Decoration" of the cationic [Th(6)(μ(3)-O)(4)(μ(3)-OH)(4)](12+) cores by anionic shells of R-COO(-) ligands (R = H, CH(3), or CH(2)Cl) terminates the oligomers and results in the formation of discrete, neutral molecular clusters. Electronic structure calculations at the density functional theory level predicted that the most energetically favorable positions for the protons on the hexanuclear core result in the cluster with the highest symmetry with the protons separated as much as possible. The synthesis, structure, and characterization of the materials are reported.

It was recently reported ( J. Chem. Theory Comput. 2015 , 11 , 2036 - 2052 ) that the coupled cluster singles and doubles with perturbative triples method, CCSD(T), should not be used as a benchmark tool for the prediction of dissociation energies (heats of formation) for the first row transition metal diatomics based on a comparison with the experimental thermodynamic values for a set of 20 diatomics. In the present work the bond dissociation energies as well as the heats of formation for those diatomics have been calculated by the Feller-Peterson-Dixon approach at the CCSD(T)/complete basis set (CBS) level of theory including scalar relativistic corrections and correlation of the outer shell of core electrons in addition to the valence electrons. Revised experimental values for the hydrides are presented that are based on new heterolytic R-H bond dissociation energies, which are needed for analysis of the mass spectrometry experiments. The agreement between the calculated bond dissociation energies and the revised experimental values of the hydrides is good. Good agreement of the calculated bond dissociation energies/heats of formation is also found for most of the chlorides, oxides, and sulfides given the experimental error bars from experiment and those of the transition metal atoms in the gas phase. Thus, reliable results can be achieved by the CCSD(T) method at the CBS limit. The use of PW91 orbitals for the CCSD(T) calculations improves the predictions for some compounds with large T diagnostics at the HF-CCSD(T) level. The optimized bond distances and calculated vibrational frequencies for the diatomics also agree well with the available experimental values.

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.

Electrocatalysis is evolving as a competitive alternative to conventional heterogeneous catalysis for the conversion of platform chemicals from biomass. Here, we demonstrate the electrocatalytic conversion of cis,cis-muconic acid, a fermentation product, to trans,trans-muconic acid, trans-3-hexenedioic acid, and adipic acid used for the production of biobased polyamides and polyesters such as nylon, nylon derivatives, and polyethylene terephthalate (PET). The electrocatalytic hydrogenation in this work considers a wide range of early, late, and post-transition metals (Cu, Fe, Ni, Mo, Pb, Pd, Sn, and Zn) with low and high hydrogen overpotentials, and varying degrees of metal hydrogen binding strengths. The binding strength was determined to be an important factor for the conversion rate, faradaic efficiency, and product distribution. Selectivities are also discussed in relation to thermodynamic data, which suggests the possibility to tune the kinetics of the reaction to allow for the variable production of multiple biobased monomers.