Normal-to-Abnormal Rearrangement and NHC Activation in Three-Coordinate Iron(II) Carbene Complexes

作者：Day Benjamin M; Pugh Thomas; Hendriks Daniel; Guerra Celia Fonseca; Evans David J; Bickelhaupt F Matthias^*; Layfield Richard A

来源：Journal of the American Chemical Society, 2013, 135(36): 13338-13341.

DOI：10.1021/ja408589p

The %26apos;normal%26apos; three-coordinate iron-NHC complex [(IPr)Fe(N%26apos;%26apos;)(2)] (N %26apos;%26apos; = N(SiMe3)(2)) rearranges to its abnormal NHC analogue [(aIPr)Fe(N %26apos;%26apos;)(2)] (6) on heating, providing a rare abnormal iron-aNHC complex, and the first such three-coordinate complex. The tert-butyl-substituted complex [((IBu)-Bu-t)Fe(N%26quot;)(2)] (4) undergoes a thermal decomposition that has not previously been observed in iron-NHC chemistry, resulting in the bis(imidazole) complex [((t)BuIm)(2)Fe(N %26apos;%26apos;)(2)] (7). A mechanism that involves consecutive C-H and C-N activation is proposed to account for the formation of 7.

• 出版日期2013-9-11