Synthesis, structure and bonding of hexaphenyl thorium(IV): observation of a non-octahedral structure

Abstract

Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG geförderten) Allianz- bzw. Nationallizenz frei zugänglich.This publication is with permission of the rights owner freely accessible due to an Alliance licence and a national licence (funded by the DFG, German Research Foundation) respectively.We report herein the synthesis of the first structurally characterized homoleptic actinide aryl complexes, [Li(DME)(3)](2)[Th(C6H5)(6)] (1) and [Li(THF)(12-crown-4)](2)[Th(C6H5)(6)] (2), which feature an anion possessing a regular octahedral (1) or a severely distorted octahedral (2) geometry. The solid-state structure of 2 suggests the presence of pseudo-agostic ortho C-H center dot center dot center dot Th interactions, which arise from sigma(C-H) -> Th(5f) donation. The non-octahedral structure is also favoured in solution at low temperatures.DFG, EXC 314, Unifying Concepts in Catalysi