Room‐Temperature Functionalization of N₂ to Borylamine at a Molybdenum Complex

Abstract

Intermolecular, stepwise functionalization by BH bonds of a (triphosphine)Mo -nitrido complex generated by N splitting is reported. The imido-hydride and di-hydride-amido Mo complexes have been isolated and characterized. Addition of PinBH to the [Mo(H) (N(BPin) )] complex at room temperature results in the liberation of borylamines from the metal center.

Metal‐Ligand Cooperative Synthesis of Benzonitrile by Electrochemical Reduction and Photolytic Splitting of Dinitrogen

“…Catalytic protocols are only known for trisilylamine . Nitriles, isocyanates, silylamines, and borylamines have been synthesized within stoichiometric, cyclic reaction sequences, which allow for evaluating strategies to offset the extremely strong N≡N bond (225 kcal mol −1 ), enable E−N (E=C, Si, B) bond formation and deliver six reduction equivalents. All reported “synthetic cycles” proceed through initial N 2 cleavage into nitride complexes.…”

Frustrated Lewis Pair Chemistry Enables N2 Borylation by Formal 1,3‐Addition of a B−H Bond in the Coordination Sphere of Tungsten

“… a) 1,2‐E−H bond addition across M−N bonds in strongly activated N 2 complexes (NPN=(PhNSiMe 2 CH 2 ) 2 PPh, Cp′=1,2,4‐trimethylcyclopentadienyl, Cp*=1,2,3,4,5‐pentamethylcyclopentadienyl) . b) Frustrated Lewis pair (FLP)‐inspired functionalization of N 2 .…”

Functionalization of N2 via Formal 1,3‐Haloboration of a Tungsten(0) σ‐Dinitrogen Complex

“…For example, reacting end‐on coordinated N 2 compounds of Mo, W or Fe with B(C 6 F 5 ) 3 leads to Lewis acid‐base adduct formation between the highly electrophilic borane and terminal N atom of the dinitrogen complex [6e,h] . Conversely, reactions with hydroboranes and ‐silanes either lead to 1,2‐/1,3‐addition products [6, 7] or boryl/silyl amines (Scheme 1 a/b), [6d,i] driven by the hydridic character of the B/Si−H bonds and formation of strong N−B and N−Si bonds in the products. In fact, N−Si bond formation has become a popular strategy for converting dinitrogen into ammonia equivalents [7h,i] .…”