Bismuthanides and Bismuthanediides − Synthesis and Structural Characterization of [R2Bi] and [(RBi)12Na21]3 Salts with Bulky Silyl Substituents

Abstract

Keywords: Bismuth / Lithium / Sodium / Silicon / Cluster compounds The reaction of bismuth trihalides with the bulky alkali metal silanides [(THF) 3 LiSi(SiMe 3 ) 3 ] and [(THF) 2 NaSi(CMe 3 ) 3 ] affords the cyclotetrabismuthanes (RBi) 4 1 and 3, the alkali metal bismuthanides [Li(THF) 4 ][Bi{Si(SiMe 3 ) 3 } 2 ](2) and Na(THF) 3 [Bi{Si(CMe 3 ) 3 }] 2 (4) and the bismuthanediide Na 3 (THF) 14 [Na 21 {BiSi(CMe 3 ) 3 } 12 ] (5). Compound 2 features a two-coordinate bismuth atom. The core of 5 is a Bi 12 icosa-

Organometallic Compounds with Homonuclear Bonds between Bismuth Atoms, 70 Years after Paneth' Report on the Violet Dimethyl Bismuth Compound

“…Bulky silyl and stannyl substituents, R ϭ (Me 3 C) 3 Si, (Me 3 Si) 3 Si, (Me 3 Si) 3 Sn were used by Linti et al for the stabilisation of bismuth rings [9,45]. The rings form in reactions between BiBr 3 and silyl or stannyl alkali metal reagents which serve not only as source for the substituents at Bi but also as reducing agents.…”

Oligosilanylated Antimony Compounds

“… 7 It should be noted that exactly the same type of chemistry was also reported with bismuth. 5 , 6 , 8 …”

Reprint of “Coordination chemistry of homoatomic ligands of bismuth, selenium and tellurium”

“…These were subject to a recent review [72]. As a singularity in bismuth chemistry, the [(RBi) 12 Na 20 ] 4− (R = Si(CMe 3 ) 3 ) anion should be mentioned, which comprises an icosahedron of bismuth atoms (Bi Bi > 520 pm) inside a pentagon dodecahedron of sodium atoms (Na Na > 350 pm; Bi Na > 317 pm) and might be seen as a link to intermetallic bismuthides [73].…”