The catalytic fixation of N by molecular Fe compounds is a rapidly developing field, yet thus far few complexes can effect this transformation, and none are selective for NH production. Herein we report that the simple Fe(0) complex Fe(EtPCHCHPEt)(N) (1) is an efficient catalyst for the selective conversion of N (>25 molecules N fixed) into NH, attendant with the production of ca. one molecule of NH. Notably, the reductant (CoCp*) and acid (PhNHOTf) used are considerably weaker than conventional chemical H and e sources used in previous demonstrations of N turnover by synthetic Fe compounds. These results show that the direct catalytic conversion of N to the hydrazine oxidation state on molecular Fe complexes is viable and that the mechanism of NH formation by such systems may proceed via Fe-NH intermediates.
The first cationic Fe silyldiazenido complexes, [Fe(PP)2(NN–SiMe3)]+[BArF4]− (PP = dmpe/depe), have been synthesised and thoroughly characterised. Computational studies show the compounds to be useful structural and electronic surrogates for the more elusive [Fe(PP)2(NN–H)]+, which are postulated intermediates in the H+/e− mediated fixation of N2 by Fe(PP)2(N2) species
“Frustrated
Lewis pairs” (FLPs) continue to exhibit
unique reactivity for the reduction of organic substrates, yet to
date, the catalytic hydrogenation of an ester functionality has not
been demonstrated. Here, we report that iPr3SnNTf2 (1-NTf2; Tf = SO2CF3) is a more potent Lewis acid than the previously studied iPr3SnOTf; in an FLP with 2,4,6-collidine/2,6-lutidine (col/lut),
this translates to faster H2 activation and the catalytic
hydrogenolysis of an ester bond by a main-group compound, furnishing
alcohol and ether (minor) products. The reaction outcome is sensitive
to the steric and electronic properties of the substrate; CF3CO2Et and simple formates (HCO2Me and HCO2Et) are catalytically reduced, whereas related esters CF3CO2
nBu and CH3CO2Et show only stoichiometric reactivity. A computational case
study on the hydrogenation of CF3CO2Et and CH3CO2Et reveals that both share a common mechanistic
pathway; however, key differences in the energies of a Sn-acetal intermediate
and transition states emerge, favoring CF3CO2Et reduction. The alcohol products reversibly inhibit 1-NTf2/lut via formation of resting-state species 1-OR/[1·(1-OR)]+[NTf2]−; however, the extra energy required
to regenerate 1-NTf2/lut exacerbates the unfavorable
reduction energy profile for CH3CO2Et, ultimately
preventing turnover. These findings will assist the design of future
main-group catalysts for ester hydrogenation, with improved performance.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.