Synthesis and characterization of an homologous series of bis(amido)diazadipnictetidines (Pnict = P, As, Sb, Bi)

Abstract

Spectroscopic and structural features are presented for the first homologous series of diazadipnictetidines, which have the general formula [DipNPnN(H)Dip]2 (Pn = P, As, Sb, Bi; Dip = 2,6-diisopropylphenyl). The compounds are obtained from a general reaction of the corresponding halopnictine with excess LiN(H)Dip, which was previously reported for [DipNBiN(H)Dip]2. However, isolation is improved by the introduction of LiN(H)-t-Bu (at the appropriate stoichiometry) following the addition of LiN(H)Dip. The intermediate steric presence of the Dip substituent is suitable to support the heterocatenate framework for all homologues. This is in contrast to the small substituents (e.g. alkyl), which enable both bis- and tris-amination, and the larger substituent (Mes* = tri-tert-butylphenyl), which can impose coordinative unsaturation (aminoiminopnictine) for the smaller congeners (P and As).Key words: phosphorus, arsenic, antimony, bismuth, phosphazanes, phosphetidines, synthesis, structures, spectroscopic characterization.