The formation of halogen bonds from iodopentafluorobenzene and 1-iodoperfluorohexane to a series of bis(η(5)-cyclopentadienyl)metal hydrides (Cp2TaH3, 1; Cp2MH2, M = Mo, 2, M = W, 3; Cp2ReH, 4; Cp2Ta(H)CO, 5; Cp = η(5)-cyclopentadienyl) is demonstrated by (1)H NMR spectroscopy. Interaction enthalpies and entropies for complex 1 with C6F5I and C6F13I are reported (ΔH° = -10.9 ± 0.4 and -11.8 ± 0...

Product contamination by gas-phase nucleation within the processing environment often limits the deposition rate that can be obtained during chemical vapor deposition (CVD) of materials for microelectronics applications. A fundamental understanding of how these particles nucleate and grow may allow us to enlarge the process envelope, providing higher growth rates without particle contamination....

Quantum chemical calculations predict the existence of new molecular species with general formula MH12, where M is a group 6 atom. The previous MHn species had n values up to 9. The new systems with n = 12 would be a new record for metal hydrides.

We report highly chemo- and regioselective reductive transpositions of methyl carbonates to furnish olefin products with complementary regioselectivity to that of established Pd-catalysis. These Rh- and Ir-catalysed transformations proceed under mild conditions and enable selective deoxygenation in the presence of functional groups that are susceptible to reduction by metal hydrides.

Cyclometalation of [Cp*IrCl(2)](2) with ketimine ligands generated very active catalysts for transfer hydrogenation of imines as well as reductive amination. The synthesis and X-ray diffraction structures of three such complexes are disclosed in this paper. The hydrides of two complexes, key intermediates in hydrogenation, have been isolated and their structures determined by X-ray diffraction ...

The FeMoco of nitrogenase is an iron-sulfur cluster with exceptional bond-reducing abilities. ENDOR studies have suggested that E4, the state that binds and reduces N2, contains bridging hydrides as part of the active-site iron-sulfide cluster. However, there are no examples of any isolable iron-sulfide cluster with a hydride, which would test the feasibility of such a species. Here, we describ...

Abstract The synthesis, characterisation and reactivity of two isostructural anionic magnesium calcium complexes is reported. By X‐ray neutron diffraction techniques, the hydrides are shown to exist as dimers, held together by a range interactions between anions bridging potassium cations. Unlike vast proportion previously reported dimeric group 2 hydrides, which have that bridge centres, here ...

Anion substitution is at present one of the pathways to destabilize metal borohydrides for solid state hydrogen storage. In this work, a solid solution of LiBH4 and LiCl is studied by density functional theory (DFT) calculations, thermodynamic modeling, X-ray diffraction, and infrared spectroscopy. It is shown that Cl substitution has minor effects on thermodynamic stability of either the ortho...

Intermetallic compounds based on hydrogen absorbing elements usually form stable hydrides. This is the case for PdZr2. Surprisingly, ZrPd2 does not absorb hydrogen although both compounds have the same crystal structure and satisfy the empirical geometrical criteria for hydride formation. Results of ab initio calculations reveal an unanticipated purely electronic origin. These results have impl...