Department of Chemistry, University of Miami, Coral Gables, Florida 33124, USA.
Inorg Chem. 2011 Jul 4;50(13):5864-6. doi: 10.1021/ic2007342. Epub 2011 May 18.
The reaction of Ni(COD)(2) with two equivalents of the TEMPO radical at 68 °C affords the 16 e(-) "bow-tie" complex Ni(η(2)-TEMPO)(2), 1, in 78% yield. Compound 1 reacts with tert-butyl isocyanide and phenylacetylene at room temperature to yield the 16 e(-) distorted square planar nickel complexes Ni(η(2)-TEMPO)(η(1)-TEMPO)(CN(t)Bu), 2, and Ni(η(2)-TEMPO)(η(1)-TEMPOH)(CCPh), 4, respectively. The facile reactivity of 1 is aided by the transition of the TEMPO ligand from an η(2) to η(1) binding mode. Complex 4 is an unusual example of hydrogen atom transfer from phenylacetylene to a coordinated TEMPO ligand.
二(1,5-环辛二烯)镍(0)与两当量 TEMPO 自由基在 68°C 下反应，生成 16e(-)“蝴蝶结”配合物 Ni(η(2)-TEMPO)(2)，产率为 78%。化合物 1 在室温下与叔丁基异氰酸酯和苯乙炔反应，分别生成 16e(-)扭曲的平面正方形镍配合物 Ni(η(2)-TEMPO)(η(1)-TEMPO)(CN(t)Bu)，2，和 Ni(η(2)-TEMPO)(η(1)-TEMPOH)(CCPh)，4。TEMPO 配体从η(2)到η(1)的配位模式的转变有助于 1 的高反应活性。配合物 4 是一个氢原子从苯乙炔转移到配位的 TEMPO 配体的不寻常例子。
