Mixed-valence nitride-bridged vanadium compounds. Synthesis and structure of V2(N)Cl5(TMEDA)2

Assembly of Molybdenum/Titanium μ-Oxo Complexes via Radical Alkoxide C−O Cleavage

“…We assign to this olive green complex the formula ( t BuO) 3 Mo[µ-N]Ti(NRAr) 3 , in which a nitrido nitrogen atom bridges the titanium and molybdenum centers. [75][76][77] That this species is paramagnetic is indicated by its shifted and broadened 1 H NMR signals. The formal oxidation state assignment we prefer for the complex is molybdenum(V)titanium(IV) as opposed to the alternative molybdenum(VI)titanium(III), based on EPR data (Figure 2) obtained at 103 K. Simulation (Figure 2) of the 103 K EPR spectrum of ( t BuO) 3 Mo-[µ-N]Ti(NRAr) 3 required inclusion of substantial molybdenum hyperfine coupling (a 1 ) 30, a 2 ) 40, a 3 ) 16 G).…”

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

“…[1][2][3][4][5][6][7] The few reactions of this type with a first-row transition-metal complex are limited to vanadium. [8,9] 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. [10][11][12] 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.…”

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

“…The few reactions of this type with a first‐row transition‐metal complex are limited to vanadium 8. 9 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 10–12. 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.…”