The di-tertiary butyl substituted (pseudo-)halogen bismuthanes tBu2BiX (X = Cl, Br, I, CN, N3, SCN) were obtained by different synthetic strategies. They show secondary bonding interactions in the solid state and can be used for the synthesis of ternary group 15 element compounds.

The stepwise synthesis of novel AsÀ Sb and AsÀ Bi bond containing molecules is described. The binary interpnictogen compounds tBu 2 EAs(H)tBu (E = Sb (1), P (4)) were prepared by reaction of tBu 2 ECl with tBuAs(H)Li • 1,4-dioxane. Subsequent lithiation yields the dimeric compounds [tBu 2 EAsLi(thf)tBu] 2 (E = Sb (2), E = P ( 5)). Compound 2 as well as tBu 2 SbAs(tBu)SiMe 3 (3) are not suitable as synthons for longer chains due to nonselective reactions. In contrast, compound 5 was successfully used for the preparation of chains with three (tBu 2 PAs(tBu) E'tBu 2 (E' = P (6), As (7), Sb (8), Bi ( 9)) and even four adjacent group 15 elements (tBu 2 PAs(tBu)E'' (tBu)N(H)tBu (E'' = P (12), As (13), Sb ( 14)). Finally, the diarsane (tBu 2 PAstBu) 2 ( 15) was synthesised by reaction of 5 with 1,2-dibromoethane. The obtained compounds were characterised by mass spectrometry, multinuclear NMR spectroscopy, IR spectroscopy and by single crystal X-ray diffraction in the case of 2, 5-9 and 12-15.

No abstract

The tert‐butyl‐substituted arsa‐ and stibaphosphanes tBu2EP(H)tBu (1: E = As, 2: E = Sb) were prepared by lithium chloride salt elimination. Metalation of 1 and 2 with nBuLi yielded the Li2P2 ring compounds [tBu2EP(Li·OEt2)tBu]2 (3: E = As, 4: E = Sb). By reaction of tBu2ECl (E = As, Sb) with 3 and 4, the interpnictogen chain molecules (tBu2E)2PtBu (5: E = As, 6: E = Sb) as well as tBu2SbP(tBu)AstBu2 (7) are accessible. Compound 7 is the first crystallographically characterized molecule in which a phosphorus atom is bound to both arsenic and antimony. Compounds 3–7 were characterized by single‐crystal XRD, NMR spectroscopy, IR spectroscopy and mass spectrometry.

Abstract. In this paper, the syntheses of antimony and nitrogen containing interpnictogen compounds are described. Using tBu 2 SbCl as reagent, a tert-butyl-substituted stibano amine tBu 2