Possible precursor complexes for the aerobic oxidation of benzene to phenol in CuHY zeolites were studied by QM/MM calculations. Structures limited to just one copper center were determined, in which both, benzene and dioxygen are adsorbed to and activated by the same transition metal cation. Frequency analyses reveal that these complexes can be identified by the frequency shift of the O(2) str...

This article briefly summarizes the research activities in the field of hydrogen storage in sorbent materials and reports our recent works and future directions for the design of such materials. Distinct features of sorption-based hydrogen storage methods are described compared with metal hydrides and complex chemical hydrides. We classify the studies of hydrogen sorbent materials in terms of t...

The discovery of cisplatin as a therapeutic agent stimulated a new era in the application of transition metal complexes for therapeutic design. Here we describe recent results on a variety of transition metal complexes targeted to DNA to illustrate many of the issues involved in new therapeutic design. We describe first structural studies of complexes bound covalently and non-covalently to DNA ...

We present a hybrid density functional theory (DFT) study of doping effects in α-Fe(2)O(3), hematite. Standard DFT underestimates the band gap by roughly 75% and incorrectly identifies hematite as a Mott-Hubbard insulator. Hybrid DFT accurately predicts the proper structural, magnetic, and electronic properties of hematite and, unlike the DFT+U method, does not contain d-electron specific empir...

We show that the nonlinear optical response reflects sensitively the electronic structure of transition-metal surfaces and interfaces. d and s electrons may contribute rather differently to the second harmonic generation (SHG) signal. This results from the different sensitivity of d and s electrons to surface and symmetry changes. Consequently, SHG for noble metals shows a by far larger depende...

A transition metal-catalyzed cross-coupling reaction of cyclopropenes with aryl iodides proceeds with the opening of the cyclopropene ring, affording 1,3-butadienes as the products.

Transition metal catalysis represents a relatively unexplored but potentially useful route to form bonds between main group elements. Previous work in the area of amine-borane adduct dehydrocoupling has exclusively employed late transition metal (e.g., Rh) catalysts which were found to predominantly operate via a heterogeneous mechanism. Herein, we present a new, early transition-metal-catalyze...

Palladium-catalyzed ring-opening thiocarbonylation of vinylcyclopropanes (VCPs) with thiols and carbon monoxide affords the corresponding unsaturated thioesters in moderate to excellent yields. This reaction provides a general method for the ring-opening thiocarbonylation of VCPs. It further demonstrates the utility of transition metal catalysts for the synthesis of organosulfur compounds.

The zinc hexazene complex (Me)L2Zn2(μ-1,6-Ph2-N6) 1 ((Me)L = HC[C(Me)N(2,4,6-Me3C6H2)]2) is a suitable hexazene transfer reagent in reactions with main group metal and transition metal complexes containing M-Me units. The reactions proceed with elimination of (Me)LZnMe and the resulting complexes were characterized by NMR and IR spectroscopy and single crystal X-ray diffraction (5, 8). Quantum ...