A Bismuth–Arene σ‐Complex – On the Edge of Menshutkin‐Type Complexes

Abstract

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]

Bismuth Atoms in Hydrocarbon Ligands: Bismepines as Rigid, Ditopic Arene Donors in Coordination Chemistry

“…The careful design and skillful choice of arene ligands bound to metals across large sections of the periodic table has aided important advances in a great variety of chemical research disciplines. Selected examples include the fields of coordination chemistry, − Lewis acidity, CH-activation, , olefin polymerization catalysis, , asymmetric catalysis, , catalyzed CO 2 reduction, and cancer research. ,− When molecules contain two or more arene groups as coordination sites, their geometry and relative orientation can crucially influence the coordination chemistry of such ligands. This becomes evident in ansa -arene, , corannulene, and cyclophane complexes, , for instance.…”

Organic Compounds of Bismuth: Synthesis, Structure, and Applications

“…The reactions of the organobismuth derivatives accompanied by the formation of organic compounds of nonordinary structure are very interesting. For example, the reactivity of aminobismuthane Mes*N(SiMe 3 )BiCl 2 (Mes* is 2,4,6-tri-tert-butylphe-nyl) with the organic metal derivatives was studied [90]. The synthesis of Mes*N(SiMe 3 )BiCl 2 in a yield of 33% is accompanied by the formation of the coupling product of two Mes*N(SiMe 3 )H molecules in a yield of 60% (Scheme 78).…”

Trimethylsilyl Pseudohalide Adducts of GaCl3 and B(C6F5)3

“…[20][21][22][23] Amongst many other Lewis acids, [10][11][12][13][24][25][26] GaCl 3 [27][28][29][30][31][32][33] and B(C 6 F 5 ) 3 [34][35][36][37][38][39][40] have been used in main group chemistry in the last decades. In recent years, we have frequently used GaCl 3 as Lewis acid for the generation of reactive cations by chloride abstraction [41][42][43][44][45][46][47][48][49] and in GaCl 3assisted [3 + 2] cycloaddition reactions yielding phosphorusnitrogen heterocycles. [50][51][52][53] B(C 6 F 5 ) 3 -adducts have been utilized in our group to stabilize highly labile pseudohalide entities, such as a HCN dimer (Scheme 1A), HN 3 (Scheme 1B) and HNSO (Scheme 1C).…”