Mechanism of Catalytic Aziridination with Manganese Corrole: The Often Postulated High-Valent Mn(V) Imido Is Not the Group Transfer Reagent

摘要

The reaction of ArI=NTs (Ar = 2-(tert-butylsulfonyl)benzene and Ts = p-toluenesulfonyl) and (tpfc)Mn (tpfc = 5,10,15-tris(pentafluorophenyl)corrole),1,affords the high-valent (tpfc)Mn~V=NTs,2,on stopped-flow time scale.The reaction proceeds via the adduct [(tpfc)Mn~(III)(ArlNTs)],3,with formation constant K_3 = (10 +- 2) x 10~3 L mol~(-1).Subsequently,3 undergoes unimolecular group transfer to give complex 2 with the rate constant k_4 = 0.26 +- 0.07 s~(-1) at 24.0 deg C.The complex (tpfc)Mn catalyzes [NTs] group transfer from ArlNTs to styrene substrates with low catalyst loading and without requirement of excess olefin.The catalytic aziridination reaction is most efficient in benzene because solvents such as toluene undergo a competing hydrogen atom transfer (HAT) reaction resulting in H_2NTs and lowered aziridine yields.The high-valent manganese imido complex (tpfc)Mn=NTs does not transfer its [NTs] group to styrene.Double-labeling experiments with ArlNTs and ArlNTs~(tBu) (Ts~(tBu) = (p-tert-butylphenyl)sulfonyl) establish the source of [NR] transfer as a "third oxidant",which is an adduct of Mn(V) imido,[(tpfc)Mn(NTs~(tBu))(ArlNTs)] (4).Formation of this oxidant is rate limiting in catalysis.