Actinide single-molecule magnetism has experienced steady growth over the last five years since the first discovery of slow magnetic relaxation in the mononuclear complex U(Ph(2)BPz(2))(3). Given their large spin-orbit coupling and the radial extension of the 5f orbitals, the actinides are well-suited for the design of both mononuclear and exchange-coupled molecules, and indeed at least one new...

We show that the 18-electron rule can be used to design new organometallic systems that can store hydrogen with large gravimetric density. In particular, Ti containing organic molecules such as C(4)H(4), C(5)H(5), and C(8)H(8) can store up to 9 wt % hydrogen, which meets the Department of Energy target for the year 2015. More importantly, hydrogen in these materials is stored in molecular form ...

We present the WCCR10 data set of 10 ligand dissociation energies of large cationic transition metal complexes for the assessment of approximate exchange-correlation functionals. We analyze nine popular functionals, namely BP86, BP86-D3, B3LYP, B3LYP-D3, B97-D-D2, PBE, TPSS, PBE0, and TPSSh by mutual comparison and by comparison to experimental gas-phase data measured with well-known precision....

The cationic dummy atom approach provides a powerful nonbonded description for a range of alkaline-earth and transition-metal centers, capturing both structural and electrostatic effects. In this work we refine existing literature parameters for octahedrally coordinated Mn(2+), Zn(2+), Mg(2+), and Ca(2+), as well as providing new parameters for Ni(2+), Co(2+), and Fe(2+). In all the cases, we a...

M. E. Williams,1 H. Sims,2,3 D. Mazumdar,2,3 and W. H. Butler2,3 1Department of Mathematics & Computer Science, University of Maryland Eastern Shore, Princess Anne, MD 21853, USA 2Center for Materials for Information Technology, University of Alabama, Tuscaloosa, AL 35401, USA 3Department of Physics, University of Alabama, University of Alabama, Tuscaloosa, AL 35401, USA (Received 21 July 2011;...

We report the use of isolable primary and secondary alkylcarbastannatrane nucleophiles in site-specific fluorination reactions. These reactions occur without the need for transition metal catalysis or in situ activation of the nucleophile. In the absence of the carbastannatrane backbone, alkyltin nucleophiles exhibit no activity towards fluorination. When enantioenriched alkylcarbastannatranes ...

A wide variety of experimental results and theoretical investigations in recent years have convincingly demonstrated that several transition metal oxides and other materials have dominant states that are not spatially homogeneous. This occurs in cases in which several physical interactions-spin, charge, lattice, and/or orbital-are simultaneously active. This phenomenon causes interesting effect...

The reactions of dilithium 1,2-diamidobenzene, [1,2-(HN)2C6H4]Li2 (L(1)H2)Li2, and dilithium 1,8-diamidonaphthalene, [1,8-(NH)2C10H6]Li2 (L(2)H2)Li2, with Cp2Ni and Cp2V have been used to obtain the new complexes (L(2)H2)2Ni{Li(THF)2}2 (3), (L(2)H2)3V{Li(THF)2}3 (4) and (L(1)H2)6Ni6·{[(L(1)H2)3(L(1)H)3Ni6Li(THF)](2-)·2[Li(THF)4](+)} (5), in which retention or oxidation of the initial metal(ii) ...

Within the last decades the transition metal-catalyzed cross-coupling of non-activated alkyl halides has significantly progressed. Within the context of alkyl-alkyl cross-coupling, first row transition metals spanning from iron, over cobalt, nickel, to copper have been successfully applied to catalyze this difficult reaction. The mechanistic understanding of these reactions is still in its infa...

The first examples of p-block coordination complexes of biquinoline, namely [(biq)BCl2]Cl and [(biq)BCl2]˙, were synthesized and structurally characterized. The acquired data allowed the estimation of the ligand charge state based on its metrical parameters. The subsequent use of this protocol, augmented with theoretical calculations, revealed ambiguities in the published data for transition me...