π-Conjugation in Gd13Fe10C13 and its oxycarbide: unexpected connections between complex carbides and simple organic molecules.

Carbometalates are a diverse family of solid state structures formed from transition metal (TM)-carbon polyanionic frameworks whose charges are balanced by rare earth (RE) cations. Remarkable structural features, such as transition metal clusters, are often encountered in these phases, and a pressing challenge is to explain how such features emerge from the competing interaction types (RE-TM, TM-TM, TM-C, etc.) in these systems.

New roles for icosahedral clusters in intermetallic phases: micelle-like segregation of Ca-Cd and Cu-Cd interactions in Ca10Cd27Cu2.

Despite significant progress in the structural characterization of the quasicrystalline state, the chemical origins of long- and short-range icosahedral order remain mysterious and a subject of debate. In this Article, we present the crystal structure of a new complex intermetallic phase, Ca10Cd27Cu2 (mC234.24), whose geometrical features offer clues to the driving forces underlying the icosahedral clusters that occur in Bergman-type quasicrystals.

Gd13Fe10C13: indications of Fe-Fe multiple bonding emerging from chemical frustration.

We report the synthesis and crystal structure of the carbide Gd(13)Fe(10)C(13). This compound adopts a new structure type that is remarkable for its "H"-shaped C(2)FeFeC(2) units, which have some of the shortest Fe-Fe contacts known. A bonding analysis using DFT-calibrated Hückel calculations hints that Fe-Fe multiple bonding underlies these short distances.

Primary atmospheric oxidation mechanism for toluene.

The products of the primary OH-initiated oxidation of toluene were investigated using the turbulent flow chemical ionization mass spectrometry technique at temperatures ranging from 228 to 298 K. A major dienedial-producing pathway was detected for the first time for toluene oxidation, and glyoxal and methylglyoxal were found to be minor primary oxidation products. The results suggest that secondary oxidation processes involving dienedial and epoxide primary products are likely responsible for previous observations of glyoxal and methylglyoxal products from toluene oxidation.