Trimethylsilylverbindungen der Vb‐Elemente. VII. Die Kristallstrukturen von Lithium‐bis(trimethylsilyl)bismutid · DME und Tetrakis(trimethylsilyl)dibismutan sowie Bemerkungen zur Kristallstruktur des Bis(4‐methoxyphenyl)ditellans

Abstract

Das farblose Lithium‐bis(trimethylsilyl)bismutid · DME 1 und das grüne, metallähnlich glänzende Tetrakis(trimethylsilyl)dibismutan 2 kristallisieren isotyp zu ihren jeweiligen Antimon‐Homologen [1, 2]. Nach Röntgenstrukturanalysen {1: −90°C; I42d; a = 1017,3(4); c = 3738,0(26) pm; Z = 8; Rw = 0,065; 2: + 20°C; P21/c; a = 680,9(4); b = 1704,8(13); c = 1197,9 (10) pm; β = 119,46(6)°; Z = 2; Rw = 0,084} bilden beide Verbindungen im Festkörper Ketten. Beim Bismutid 1 bauen sie sich schraubenartig aus Bismut‐ und Lithiumatomen in alternierender Abfolge auf; durch Bindung zu zwei Trimethylsilyl‐Substituenten bzw. zum Chelatliganden DME wird jeweils die Koordinationszahl 4 erreicht {LiBi 292(3); BiSi 263,3(14) pm; BiLiBi 132(1); LiBiLi 148(1); φ(LiBiLiBi) 83°}. Beim Dibismutan 2 reihen sich die BiBi‐Hanteln zu fast linearen, homonuklearen Zickzack‐Ketten mit verkürztem intermolekularem Kontakt auf; das Molekül besitzt die zentrosymmetrische Konformation {BiBi 303,5(3); Bi…︁Bi 380,4(3); BiSi 268 pm; BiBi…︁Bi 169;  BiBiSi 97,4(5) und 92,0(5)°}. Struktur und Eigenschaften von 2 werden mit denen ähnlicher Verbindungen verglichen; die bereits von Ludlow u. McCarthy [3] publizierte Kristallstruktur des braunen, grün metallisch glänzenden Bis(4‐methoxyphenyl)ditellans 5 wird im Hinblick auf sehr kurze intermolekulare Te …︁ Te‐Kontakte untersucht.

Molecular Structure and Theoretical Studies of (PPh4)2[Bi10Cu10(SPh)24]

“…Bond lengths are in the range of Bi À Bi separations reported for the dibismuthines Ph 4 Bi 2 , [17] (Me 3 Si) 4 Bi 2 , [18] [2-(Me 3 Si) 2 CH] 4 Bi 2 , [19] and (2,4,6-Me 3 C 6 H 2 ) 4 Bi 2 . [20] The atoms Bi3 and Bi6, through which the two Bi 5 chains are connected, are both in trigonal- pyramidal environments in which the corners are occupied by Bi atoms.…”

“…Examples include [BiIr 6 S 8 (Cp*) 2 ]Cl (Cp* = h 5 -C 5 Me 5 ), [12] [BiTi 2 O(OiPr) 9 ], [13] and (PPh 4 ) 3 [Bi(WS 4 ) 3 ]. [14] Ternary molecular clusters in which the cluster core consists of transition-metal, chalcogen, and 18 ], [15] and 24 ]·0.5 DME (1) was synthesized by heating a suspension of Bi(SPh) 3 , CuSPh, PPh 4 Cl, and PhSSiMe 3 in 1,2-dimethoxyethane (DME) at reflux for one hour. From the resulting orange solution, black crystals of 1 formed after several weeks.…”

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

“…[5] About 40 years later, the first lithium bismuthanide [(dme)LiBi(SiMe 3 ) 2 ] was structurally characterized. [6] MER 2 and M 2 ER (E ϭ P, As) compounds are normally prepared by metalation of phosphanes and arsanes and the lack of stable hydrogen compounds of bismuth might have caused the low interest in metalated bismuthanes; [7] only very recently was the first stable diarylbismuthane reported. [8] We report here on the reduction of bismuth halides with alkali metal silanides resulting in cyclotetrabismuthanes [9] and bismuthanides and bismuthanediides.…”

Preparation, Geometric and Electronic Structures of [Bi2Cu4(SPh)8(PPh3)4] with a Bi2 Dumbbell, [Bi4Ag3(SePh)6Cl3(PPh3)3]2 and [Bi4Ag3(SePh)6X3(PPhiPr2)3]2 (X = Cl, Br) with a Bi4 Unit

“…The bismuth atoms form a trigonal pyramid in which the apical Bi2 atom is bonded to Bi1, Bi3 and Bi4 with bond lengths of 299.9(9)-302.9(1) pm. The bond lengths in 3-5 are in the range of Bi-Bi distances reported for the dibismuthanes Ph 4 Bi 2 , [10] (Me 3 Si) 4 Bi 2 , [11] [2-(Me 3 Si) 2 CH] 4 Bi 2 [12] and α-Bi (Bi-Bi 307.2 pm, Bi-Bi-Bi 95.4°). [13] The Bi1, Bi3 and Bi4 atoms are each surrounded by two µ 2 -Se atoms of the PhSe [14] and 269 pm in [AgBr(PPh 3 ) 3 ].…”