93627-00-0Relevant articles and documents
Formation of Di-iron Hexacarbonyl Complexes of 3H-1,2-Diazepines and the Effects of Complexation on Ring Inversion and the Rate of Sigmatropic Hydrogen Migration
Argo, Carl B.,Sharp, John T.
, p. 1581 - 1587 (2007/10/02)
A number of 3H-1,2-diazepines have been synthesised by the reactions of 6,7-dihydro-1-tosyl-1,2-diazepines with base.These diazepines are in dynamic equilibrium at room temperature via sigmatropic hydrogen migrations but in some cases could be separated by h.p.l.c. at 0 deg C.The reactions of 1H-2,3-benzodiazepines, 3H-1,2-benzodiazepines and the monocyclic 3H-1,2-diazepines (9)/(10) with di-iron noncarbonyl gave the dinuclear iron hexacarbonyl complexes (12), (14), and (15)/(16), respectively, in moderate yield.The complexes were found undergo ring inversion more easily than their precursors, and activation energies were determined.The complexation of the azo group also stopped the easy sigmatropic hydrogen shift observed for (9)/(10) and this is discussed in terms of changes in electronic effect and in the structural geometry of the diazepine ring.
