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

Abstract

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)Å respectively.