Del Horno Estefanía, Jover Jesús, Mena Miguel, Pérez-Redondo Adrián, Yélamos Carlos
Departamento de Química Orgánica y Química Inorgánica, Instituto de Investigación Química "Andrés M. del Río" (IQAR), Universidad de Alcalá, 28805, Alcalá de Henares-Madrid, Spain.
Secció de Química Inorgànica, Departament de Química Inorgànica i Orgànica, Institut de Química Teòrica i Computacional (IQTC-UB), Universitat de Barcelona, Martí i Franquès 1-11, 08028, Barcelona, Spain.
Angew Chem Int Ed Engl. 2022 Aug 22;61(34):e202204544. doi: 10.1002/anie.202204544. Epub 2022 Jul 11.
Reaction of [TiCpCl ] (Cp=η -C Me ) with one equivalent of magnesium in tetrahydrofuran at room temperature affords the paramagnetic trinuclear complex [{TiCp*(μ-Cl)} (μ -Cl)], which reacts with dinitrogen under ambient conditions to give the diamagnetic derivative [{TiCp*(μ-Cl)} (μ -η : η : η -N )] and the titanium(III) dimer [{TiCpCl(μ-Cl)} ]. The structure of the trinuclear mixed-valence complexes has been studied by experimental and theoretical methods and the latter compound represents the first well-defined example of the μ -η : η : η coordination mode of the dinitrogen molecule. The reaction of [{TiCp(μ-Cl)} (μ -η : η : η -N )] with excess HCl in tetrahydrofuran results in clean NH Cl formation with regeneration of the starting material [TiCpCl ]. Therefore, a cyclic ammonia synthesis under ambient conditions can be envisioned by alternating N /HCl atmospheres in a [TiCpCl ]/Mg(excess) reaction mixture in tetrahydrofuran.
在室温下，[TiCpCl₂]（Cp = η⁵-C₅Me₅）与一当量镁在四氢呋喃中反应，得到顺磁性的三核配合物[{TiCp*(μ-Cl)}₂(μ₂-Cl)]，该配合物在环境条件下与氮气反应，生成抗磁性衍生物[{TiCp*(μ-Cl)}₂(μ₂-η²:η²:η²-N₂)]和钛(III)二聚体[{TiCpCl(μ-Cl)}₂]。已通过实验和理论方法研究了三核混合价配合物的结构，后一种化合物代表了N₂分子的μ₂-η²:η²:η²配位模式的首个明确实例。[{TiCp(μ-Cl)}₂(μ₂-η²:η²:η²-N₂)]在四氢呋喃中与过量HCl反应，生成纯净的NH₄Cl，并使起始原料[TiCpCl₂]再生。因此，通过在四氢呋喃中的[TiCpCl₂]/Mg(过量)反应混合物中交替通入N₂/HCl气氛，可以设想在环境条件下进行循环氨合成。
