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- 저자 : oz III, Salvador B. (검색결과 1 건)
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Mechanistic study of styrene aziridination by iron( <small>IV</small> ) nitrides
Crandell, Douglas ,W.,Muñ,oz III, Salvador B.,Smith, Jeremy M.,Baik, Mu-Hyun Royal Society of Chemistry 2018 Chemical Science Vol.9 No.45
<▼1><P>A combined experimental and computational investigation reveals that styrene aziridination by an iron(<SMALL>IV</SMALL>) nitride occurs by a stepwise mechanism involving multistate character.</P></▼1><▼2><P>A combined experimental and computational investigation was undertaken to investigate the mechanism of aziridination of styrene by the tris(carbene)borate iron(<SMALL>IV</SMALL>) nitride complex, PhB(<SUP><I>t</I></SUP>BuIm)<SUB>3</SUB>Fe 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 N. While mechanistic investigations suggest that aziridination occurs <I>via</I> a reversible, stepwise pathway, it was not possible to confirm the mechanism using only experimental techniques. Density functional theory calculations support a stepwise radical addition mechanism, but suggest that a low-lying triplet (<I>S</I> = 1) state provides the lowest energy path for C–N bond formation (24.6 kcal mol<SUP>–1</SUP>) and not the singlet ground (<I>S</I> = 0) state. A second spin flip may take place in order to facilitate ring closure and the formation of the quintet (<I>S</I> = 2) aziridino product. A Hammett analysis shows that electron-withdrawing groups increase the rate of reaction <I>σ</I><SUB>p</SUB> (<I>ρ</I> = 1.2 ± 0.2). This finding is supported by the computational results, which show that the rate-determining step drops from 24.6 kcal mol<SUP>–1</SUP> to 18.3 kcal mol<SUP>–1</SUP> when (<I>p</I>-NO<SUB>2</SUB>C<SUB>6</SUB>H<SUB>4</SUB>)CH 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 CH<SUB>2</SUB> is used and slightly increases to 25.5 kcal mol<SUP>–1</SUP> using (<I>p</I>-NMe<SUB>2</SUB>C<SUB>6</SUB>H<SUB>4</SUB>)CH 00000000000
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