Tl^I[C(SiMe₃)₃] – eine Alkylthallium(I)‐Verbindung mit einem verzerrten Tetraeder aus Tl‐Atomen im Festkörper

Abstract

Nur schwache Thallium‐Thallium‐Wechselwirkungen liegen in den Thallium‐Tetraedern der kristallinen Alkylthallium(I)‐Verbindung Tl[C(SiMe3)3] vor, die aus Cyclopentadienylthallium(I) und Tris(trimethylsilyl)methyllithium leicht zugänglich ist. In Lösung lassen sich nur Monomere der thermisch außerordentlich empfindlichen Verbindung nachweisen.

Tetrahedral homonuclear organoelement clusters and subhalides of aluminium, gallium and indium

“…However, the Tl-Tl distances are very long indicating only weak direct Tl-Tl interactions. In addition, in the case of the alkyl derivative [Tl-C (SiMe 3 ) 3 ] 4 the Tl 4 tetrahedron is strongly distorted with two different ranges of Tl-Tl separations (334 and 358 pm on average) (Uhl et al 1997c). Furthermore, the Tl-C bonds are tilted with respect to the cluster surface.…”

“…Organothallium compounds were also obtained by similar routes with the treatment of cyclopentadienylthallium(I), which does not form a cluster but is a cyclopentadienyl-bridged polymer (Frasson et al 1963;Dashti-Mommertz et al 1999), or thallium(I) halides with the corresponding lithium derivatives. Although tetrahedral arrangements of four thallium atoms were observed in some cases in the solid state, only very weak direct Tl-Tl van der Waals interactions exist, indicated by long Tl-Tl distances and by more or less strong deviations of the core structures from the regular tetrahedral symmetry (Uhl et al 1997c;Deacon et al 2000;Rheingold et al 1997). Another class of subhalides, digallium(II) tetrahalides containing Ga-Ga single bonds, has been employed in similar reactions; however, they produced the tetrahedral tetragallium(I) clusters by disproportionation in low yields usually (Rheingold et al 1997;Linti 1996).…”

Sodium–Potassium Alloy for the Reduction of Monoalkyl Aluminum(III) Compounds

“…The cluster [TrisM] of gallium (7), indium (8), and thallium (9) was prepared by reacting Ga Br )dioxane, InBr, and CpTl with TrisLi, respectively. The analogous aluminum compound (TrisAl) was previously prepared by reacting TrisAlI )THF with Na/K alloy (10).…”

Al22Br20⋅12 THF: The First Polyhedral Aluminum Subhalide—A Step on the Path to a New Modification of Aluminum?

“…In the last ten years the use of stabilizing ligands has enabled the synthesis of polyhedral E I compounds, whose first structurally characterized examples were [AlCp*] 4 [7] (Cp* C 5 Me 5 ), [GaC(SiMe 3 ) 3 ] 4 , [8] [InCp*] 6 , [9] and [TlC(SiMe 3 ) 3 ] 4 [10] . In the meantime a large number of such polyhedral compounds has been characterized; [11] however, hithero there were no polyhedra with halogen substituents analogous to the boron halides.…”