Monomethylation and -protonation of Lutetium Dinitrogen Complex.
J Am Chem Soc
; 146(26): 17624-17628, 2024 Jul 03.
Article
em En
| MEDLINE
| ID: mdl-38889210
ABSTRACT
Due to the highly chemically inert nature, direct activation and transformation of dinitrogen are challenging. Here, we disclose the synthesis, isolation, and derivatization of (N2)3- supported by lutetium complex. Initially, a (N2)3- radical, in [{(C5Me5){MeC(NiPr)2}Lu}2(µ2-η2η2-N2)][K(crypt)] (crypt = 2,2,2-cryptand) complex, was generated through the reduction of neutral lutetium dinitrogen complex [{(C5Me5){MeC(NiPr)2}Lu}2(µ2-η2η2-N2)] with potassium metal. Subsequently, the reaction of (N2)3- complex with methyl triflate (or triflic acid) led to the formation of an N-C (or N-H) bond, yielding the corresponding [{(C5Me5){MeC(NiPr)2}Lu}2(NN-R)(OTf)][K(crypt)] (R = Me, H, OTf = CF3SO3) as the product. Both electron paramagnetic resonance spectroscopy and density functional theory analyses support the radical character of the NN-Me unit. The Lu-N bonds in the (NN-Me)â¢2- radical complex are predominantly ionic, with 77% of the unpaired electron localized on the (NN-Me) fragment. Moreover, the geometry of the pure organic radical (NN-Me)â¢2-, optimized by double-hybrid density functional theory, closely matches that of the (NN-Me)â¢2- lutetium complex.
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MEDLINE
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En
Ano de publicação:
2024
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Article