Alkaline Earth Metal Organoamide Complexes Displaying Close Ae-F(C) (Ae = Ca, Mg) Interactions

作者：Deacon Glen B^*; Junk Peter C; Kelly Rory P

来源：Australian Journal of Chemistry, 2013, 66(10): 1288-1296.

DOI：10.1071/CH13228

Protolysis of [Ca{N(SiMe3)(2)(thf)(2)] (thf = tetrahydrofuran) with the N,N-dialkyl-N%26apos;-2,3,5,6-tetrafluorophenylethane1,2-diamines, p-HC6F4NH(CH2)(2)NR2 ((LH)-H-R; R = Me or Et), yields [Ca(p-HC6F4N(CH2)(2)NR2)(2)(thf)(2)], whilst protolysis of di-n-butylmagnesium by the same amines yields [Mg(p-HC6F4N(CH2)(2)NR2)(2)] complexes. X-Ray crystal structures show that the calcium derivatives contain eight-coordinate calcium atoms, with tridentate (N,N%26apos;,o-F) coordination of the organoamide ligands and cisoid thf donors. It is noteworthy that the Ca-F(C) bond lengths are shorter than the Ca-NR2 bond lengths. By contrast, magnesium forms centrosymmetric, six-coordinate, homoleptic complexes, in which the Mg-NR2 bond lengths are shorter than the Mg-F(C) bond lengths. F-19{H-1} NMR spectra of the R =

• 出版日期2013