Heterobimetallic Nitride Complexes from Terminal Chromium(V) Nitride Complexes: Hyperfine Coupling Increases with Distance

摘要

Terminal nitride complexes of rhenium, osmium and molybdenum can form complexes with either alkylating agents, Lewis acidic metal halides, or low-valent, coordinatively unsaturated metal complexes The few reactions of this type with a first-row transition-metal complex are limited to vanadium. Recently, the nitride chemistry of the chromium(V) cation has been significantly expanded by introduction of a preparative route which is based on nitrogen transfer from [Mn(N)(salen)] (salen = N,N'-bis(salicylidene)ethylenediamine) to the chromium(V) cation. With a range of chromium nitride complexes at hand we have investigated their reactivity and found that nucleophilicity is a general property which can be observed during formation of imide complexes with, for example, the trityl cation, tris-(pentafluorophenyl)boron, and methyl triflate. In addition we report that terminal chromium(V) nitride complexes coordinate through the nitride ligand to low-valent complexes of the platinum metals. These compounds are possible precursors to bimetallic nitride phases which are gaining in importance as heterogeneous catalysts in, for example, the Haber-Bosch process.