Double α,α CH Bond Insertion into sp3 CH2 Moiety: Synthesis of a Fe Carbene bis-Hydride Dinitrogen Complex.

Reduction of high spin paramagnetic complex [(κ2-P, P’-PCH2PCy)FeCl2] 2 by two electrons under N2 resulted in the formation of two isomeric low spin diamagnetic complexes 3trans and 3cis [Fe(κ3-P,C,P’-PCPCy)(H)2(N2)]. Cristallization...

Ammonia Formation Catalyzed by Dinitrogen-Bridged Dirhenium Complex Bearing PNP-Pincer Ligands under Mild Reaction Conditions

A series of rhenium complexes bearing a pyridine-based PNP-type pincer ligand are synthesized from rhenium phosphine complexes as precursors. A dinitrogen-bridged dirhenium complex bearing the PNP-type pincer ligands catalytically converts dinitrogen into ammonia in the reaction with KC₈ as a reductant and [HPCy₃]BAr^F₄ (Cy = cyclohexyl, Ar^F = 3,5-(CF₃)₂C₆H₃) as a proton source at –78 °C to afford 8.4 equiv of ammonia based on the rhenium atom of the catalyst. The rhenium-dinitrogen complex also catalyzes silylation of dinitrogen in the reaction with KC₈ as a reductant and Me₃SiCl as a silylating reagent under ambient reaction conditions to afford 11.3 equiv of tris(trimethylsilyl)amine based on the rhenium atom of the catalyst. These results demonstrate the first successful example of catalytic nitrogen fixation under mild reaction conditions by using rhenium-dinitrogen complexes as catalysts.

Ammonia Formation Catalyzed by Dinitrogen-Bridged Dirhenium Complex Bearing PNP-Pincer Ligands under Mild Reaction Conditions

A series of rhenium complexes bearing a pyridine-based PNP-type pincer ligand are synthesized from rhenium phosphine complexes as precursors. A dinitrogen-bridged dirhenium complex bearing the PNP-type pincer ligands catalytically converts dinitrogen into ammonia in the reaction with KC₈ as a reductant and [HPCy₃]BAr^F₄ (Cy = cyclohexyl, Ar^F = 3,5-(CF₃)₂C₆H₃) as a proton source at –78 °C to afford 8.4 equiv of ammonia based on the rhenium atom of the catalyst. The rhenium-dinitrogen complex also catalyzes silylation of dinitrogen in the reaction with KC₈ as a reductant and Me₃SiCl as a silylating reagent under ambient reaction conditions to afford 11.3 equiv of tris(trimethylsilyl)amine based on the rhenium atom of the catalyst. These results demonstrate the first successful example of catalytic nitrogen fixation under mild reaction conditions by using rhenium-dinitrogen complexes as catalysts.

Time-resolved infra-red spectroscopy reveals competitive water and dinitrogen coordination to a manganese(i) carbonyl complex

Photolysis of [Mn(C^N)(CO)4] (C^N = bis-(4-methoxyphenyl)methanimine) in heptane solution results in ultra-fast CO dissociation and ultimate formation of a rare Mn-containing dinitrogen complex fac-[Mn(C^N)(CO)3(N2)].

Structural characterization of molybdenum–dinitrogen complex as key species toward ammonia formation by dispersive XAFS spectroscopy

Dispersive XAFS (DXAFS) was used for the structural characterization of a hardly-isolatable molybdenum–dinitrogen complex bearing a PNP-type pincer ligand.