Bismuthenium-pnictonium dications [R′BiPnR3]2+ (Pn = As, Sb) containing carbenoid bismuth centers and rare Bi–Sb bonds

Abstract

Arsine and stibine ligands stabilize bismuthenium cations and bismuthetidinium dications to give compounds containing As-Bi bonds and Sb-Bi bonds. The first enium-onium bonding environments in dications of the form [R'BiPnR(3)](2+) (Pn = As, Sb) contain the first definitive examples of carbenoid bismuth centers.

Stannylphosphonium Cations

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Compounds containing bonds between heavy p-block elements (E) are promising as materials that exhibit new properties, [1] however synthetic approaches to EÀE' bonds are limited. We have exploited coordination chemistry between pnictogen (Pn = P, As, Sb, or Bi) elements as a versatile and high yield method to form new or rare Pn À Pn' bonds, [2][3][4][5][6][7][8] as in the general reaction Equation (1) involving the combination of a pnictine, a chloropnictine and a halide abstracting agent (e.g. A = Me 3 SiOSO 2 CF 3 , AlCl 3 ).

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Neutral and Cationic β-Ketoiminato Bismuth Complexes

“…Bi ··· Cl contacts are in the range of 3.163 to 3.539 Å. Cationic bismuth complexes having Bi ··· Cl contacts with anions are known in the literature. These include [Bi{Me 2 Si(NAr) 2 }][ M Cl 4 ] ( M = Al, Ga),[2b] [Bi{Me 2 Si(N t Bu) 2 }][AlCl 4 ],[2d] [(Ph 3 Sb)BiCl 2 ][AlCl 4 ], and [(C 6 Me 6 )BiCl 2 ][AlCl 4 ] . The Bi ··· Cl distances in 4 are found within the range observed in above four compounds.…”

Covalently bonded compounds of heavy group 15/16 elements – Synthesis, structure and potential application in material sciences

“…The cation [MesTe(SbPh 3 )] + interacts in the trans position with the π system of the mesityl group of an adjacent cation [MesTe(SbPh 3 )] + as was observed for [Cl 2 Bi(SbPh 3 )]AlCl 4 ·toluene, in which the toluene molecule coordinates to the Bi atom in the trans position of Ph 3 Sb(Fig. 24) [141]. Solid state structure of the cation [MesTe-SbPh 3 ] + [139].…”