Abstract
The first molecular compound with all five pnictogens was obtained by a multi‐step reaction. Lithiation of the (bisamido)diazadiarsetidine (tBuNAs)2(tBuNH)2 in aliphatic solvents leads to the dimeric metallated species [(tBuNAs)2(tBuNLi)2]2 (12). Upon reactions with AsCl3, SbCl3 and BiCl3 the polycyclic compounds [(tBuNAs)2(tBuN)2]PnCl (Pn=As (2), Sb (3), Bi (4)) can be obtained. Conversion of 2–4 with [tBu2SbP(tBu)Li(OEt2)]2 leads to the remarkable interpnictogens [(tBuNAs)2(tBuN)2]PnP(tBu)SbtBu2 (Pn=As (5), Sb (6), Bi (7)), whereby 7 is the first example of a molecule containing all five Group 15 elements. The compound with adjacent AsNBiPSb‐chains is surprisingly stable and does not show high sensibility against light as the labile Bi−P bond might suggest.
Highlights
Molecular compounds that contain different Group 15 elements are of general interest due to their specific bonding situations and reactivity
Pentavalent bismuth species like Ph3Bi(N=PPh3)2 remain exceptional within this class of compounds.[16]
Diazadibismetidines like [Bi2(NtBu)4Li2], [PhBi(m-NtBu)]2 or [DippNHBi(m-NDipp)]2 are known as well but only a little work has been done in this field up to now.[29,30,31]
Summary
Molecular compounds that contain different Group 15 elements are of general interest due to their specific bonding situations and reactivity. 3 and 4 have already been prepared in the past, but for 4 no analytical data were provided.[32,33] NMR spectroscopy in C6D6 of the compounds 2–4 was conducted at room temperature and for the 1H nucleus (300 MHz) the results unexpectedly differ (see Supporting Information for details).
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