Synthesis, structure and properties of trivalent and pentavalent tricarbabismatranes

Abstract

The first trivalent and pentavalent tricarbabismatranes were synthesized by the reaction of N(CH2{2-LiC6H4})3 with BiCl3 and subsequent reaction with XeF2, respectively. The trivalent bismatrane was easily oxidized by air, while...

Fusing Triphenylbismuth and PnPh3 (Pn = P–Bi): Synthesis, Isolation, and Characterization of 9-Bisma-10-Pnictatriptycenes

“…The resonances for the carbon atoms attached to the bismuth atom are visible as broad singlets at δ = 168.2 (2-P), 167.9 (2-As), 171.7 (2-Sb), and 174.6 ppm (2-Bi), which is at significantly lower field than the respective signals in a recently reported tricarbabismatrane (δ = 159.3 ppm) 48 and the literature-known 2,3,6,7,14,15-hexamethyl-9-phospha-10-bismatriptycene (163.4 ppm) 19 as well as 9-bisma-10-silatriptycene (δ = 157.2 ppm). 21 Upon triptycene formation, the resonances for the carbon atoms bound to the second pnictogen atoms can be found at similar chemical shifts as the signals for the respective homodipnictatriptycenes (II−P, 145.3; 46 2,3,6,7,14,15-hexamethyl-9,10-diphosphatriptycene, 142.9; 18 II−As, 146.1; 49 2,3,6,7,14,15-hexamethyl-9,10-distibatriptycene, 146.0 ppm 17 ) but are shifted toward lower magnetic field (2-P, δ = 144.8; 2-As, 149.2; 2-Sb, 152.3; 2-Bi, 174.6 ppm) compared to their precursors 1-Pn (see Table 1).…”

Extending Chirality in Group XIV Metallatranes

“…Characteristic features of metallatranes are the intramolecular N→M (M = metal, metalloid) coordination and the right- or left-handed (Δ and Λ) propeller-type stereochemistry of the atrane cages. Consequently, investigating the strength of this interaction in dependence of variation of E and R but also of the amino alcohol chain length and its structural variation has been one focus of the early studies. Inorganic metallatranes contain no C-bound substituent occupying the axial position of a trigonal bipyramid and one amino alkoxide moiety forming the atrane cage …”