Preparation of the nitrenes ReF5(NF), ReF5(NCl), and ReF5(NBr). X-Ray crystal structures of ReF5(NF) and ReF5(NCl)

The action of Si(CH3)3(N3) on ReF6 leads to the nitride fluoride ReF4N in low yield together with a mixture which appears to contain ReF3N. Treatment of either of these materials with XeF2, ClF3, or BrF3 as appropriate gives the ‘nitrenes’ ReF5(NF), ReF5(NCl), and ReF5(NBr); other methods of preparing ReF5(NCl) and ReF5(NBr) are also described. From single-crystal measurements it has been shown that in ReF5(NF) and ReF5(NCl) the ReNF and ReNCl bonds respectively are nearly linear; the short N–F and N–Cl bond lengths are 1.257(13) and 1.56(2)A respectively.