The reaction of lithium N-trimethylsilyl-amides of the type RN(SiMe3)Li with bismuth(iii) chloride yielded mono-, di- or triaminobismuthanes depending on the sterical demand of the anilide ligand R and the used stoichiometry. For the bulky Mes* substituent the reaction with BiCl3 resulted in the formation of a C-C coupling product as the main product besides a small amount of the expected Mes*N(SiMe3)BiCl2.

This work describes the synthesis and full characterization of elusive chloropnictenium ion salts of the type [(R)Ar*N(SiMe)ECl][A] ((R)Ar* = 2,6-(CHPh2)-4-R-C6H2, R = Me, tBu; E = Sb, Bi; A(-) = GaCl4, Al(OCH(CF3)2)4). In these species the cation is significantly stabilized by weak arene interactions to flanking phenyl groups of the (R)Ar* moiety. In this context the bonding situation has been studied by computational means and the reactivity towards the Lewis base 4-dimethylaminopyridine (dmap) was investigated.

The reaction of HN 3

A dichloro-cycloazatriphosphane that incorporates a cyclic NP backbone could be synthesized using knowledge gained from the chemistry of N P and P ring systems. It fills the gap between the congeneric compounds [ClP(μ-NR)] and [ClP(μ-PR)] (R=sterically demanding substituent), and thus contributes to the systematic development of nitrogen-phosphorus chemistry in general. The title compound was studied with respect to its formation via a labile aminodiphosphene, which readily underwent different rearrangement reactions depending on the solvent. All compounds were fully characterized by experimental and computational methods.

Mes*N(SiMe 3 )BiCl 2 (1, Mes* = 2,4,6-tri-tert-butylphenyl) can be referred to as a hidden iminobismuthane, Mes*N=BiCl, which was thought to be generated in-situ upon Me 3 SiCl elimination triggered by a Lewis acid such as GaCl 3 . Therefore, the reactivity of aminobismuthane 1 was studied to find a synthesis route for the formation of a tetrazabismuthole in a [3+2] cycloaddition reaction with a covalently bound azide. However, reaction of 1 with GaCl 3 cleanly led to [Mes*N(SiMe 3 )-BiCl][GaCl 4 ] (2[GaCl 4 ]), a compound with a Bi-arene σ-complex. Utilizing Ag[WCA] salts (WCA = weakly coordinating anion) for [a]