Synthesis of a Stable Metallic Niobium Oxide Molecular Sieve and Subsequent Room Temperature Activation of Dinitrogen

Mesoporous niobium oxide was treated at room temperature with bis(toluene) niobium to make a new black material that exhibits metallic properties. The metallic behavior is attributed to low‐valent Nb^II in the walls of the porous structure and is fully supported by strong emissions at the Fermi level, variable temperature resistivity measurements, and temperature‐independent paramagnetism. These materials possess higher conductivities than reported for any molecular sieve and also represent the first example of a metallic oxide‐based molecular sieve. For comparison, the conductivity is almost 10 000 times greater than the highest value measured for an open structured mesoporous material. Treatment at room temperature with dinitrogen leads to formation of a thin nitride coat on the surface. Cleavage of dinitrogen is an extremely rare and important reaction that typically requires very forcing conditions in the solid state (high temperatures in excess of several hundred degrees, argon plasmas, etc.) or low‐valent coordinatively stressed metal centers in the homogeneous phase. This is the first example of a molecular sieve mediating this process and because of the controlled porosity and high surface areas of these materials they are ideal candidates for model studies for nitrogen reduction and catalytic nitrogen incorporation into organic compounds. Since porous materials are often the catalytic support of choice for industrial processes, these materials may lead to the development of commercial nitrogen incorporation processes.