Synthesis of silyl iron dinitrogen complexes for activation of dihydrogen and catalytic silylation of dinitrogen

Abstract

Three novel iron dinitrogen hydrides, [FeH(ⁱPr-PSi^MeP)(N₂)(PMe₃)] (1), [FeH(ⁱPr-PSi^PhP)(N₂)(PMe₃)] (2), and [FeH(ⁱPr-PSi^Ph)(N₂)(PMe₃)] (3), supported by a silyl ligand are synthesized for the first time by changing the electronic effect and steric hindrance of the ligands through the reaction of ligands L1–L3 with Fe(PMe₃)₄ in a nitrogen atmosphere. The ligands containing an electron-donating group with large steric hindrance on the phosphorus atom are beneficial for the formation of dinitrogen complexes. A penta-coordinate iron hydride [FeH(ⁱPr-PSi^Ph)(PMe₃)₂] (4) was formed through the reaction of ligand L3 with Fe(PMe₃)₄ in an argon atmosphere under the same conditions. The reactions between complexes 1–3 with an atmospheric pressure of dihydrogen gas resulted in Fe(II) dihydrides, [(ⁱPr-PSi^Me(μ-H)P)Fe(H)₂(PMe₃)] (5), [(ⁱPr-PSi^Ph(μ-H)P)Fe(H)₂(PMe₃)] (6) and [(iPr-PSi^Ph(μ-H))Fe(H)₂(PMe₃)₂] (7), with an η²-(Si–H) coordination. The isolation of dihydrides 5–7 demonstrates the ability of the dinitrogen complexes 1–3 to realize the activation of dihydrogen under ambient temperature and pressure. The molecular structures of complexes 1–7 were elucidated by single crystal X-ray diffraction analysis. The iron dinitrogen hydrides 1–3 are effective catalysts for the silylation of dinitrogen under ambient conditions and among them 3 is the best catalyst.