Structurally Characterized Bi Cations

The first known Bi cations [43] were synthesized in acidic NaAlCl4/AlCl3 melts by reaction of Bi metal and BiCl3 with AICI3 as the chloride acceptor or by direct fusion of Bi metal and BiCl3 as shown in Eqs. 1-3  

Only recently [42a, 46, 47] it was found that the presence of an electron rich transition metal such as Ir in melts of BiX3 (X = Cl, Br) and Bi metal leads to the formation of large isolated and weakly coordinating cluster anions of type [IrBi Xn]-and [IrBi Xn]2- that stabilize the smaller hitherto unknown Bis+ and Bi 2+ in the interstices of the anion lattice (Eq. 5). 

A closely related heteronuclear cation in this context is the Bi8Si 23 1 cation found in the phase Bii4Si2MI12 (M = Rh, Ir) together with the [MBi6li213 counterion [64], For other related species see Refs. [65-68], 

Sb53+ powder data of Sb5[GaCl4]3 [44] [44] elemental analysis [44] [44] 

9 Neutron diffraction ofliquid Bi5[AlCl4]3 [51]. b Bi6X7 band structure. )Bi37lnBr4g band structure. 

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