Convenient access to the anhydrous thorium tetrachloride complexes ThCl4(DME)2, ThCl4(1,4-dioxane)2 and ThCl4(THF)3.5 using commercially available and inexpensive starting materials

Abstract

Anhydrous thorium tetrachloride complexes ThCl(4)(DME)(2), ThCl(4)(1,4-dioxane)(2), and ThCl(4)(THF)(3.5) have been easily accessed from inexpensive, commercially available reagents under mild conditions and serve as excellent precursors to a variety of thorium(iv) halide, alkoxide, amide and organometallic compounds.

Exploring Synthetic Routes to Heteroleptic UIII, UIV, and ThIV Bulky Bis(silyl)amide Complexes

“…With heteroleptic U III complexes in hand, we turned our attention to the synthesis of heteroleptic An IV complexes. The separate reactions of UCl 4 and [ThCl 4 (THF) 3.5 ] with 1.5 or 2 equiv. of dimeric [{K(µ‐N**)} 2 ] ∞ in THF gave complex mixtures of products, from which crystals of the cyclometallated complexes [An(N**){N(SiMe 2 t Bu)(SiMe t BuCH 2 ‐κ 2 ‐ N , C )}(µ‐Cl)] 2 ( 7‐An , An =U, Th) and [Th(N**) 2 {N(SiMe 2 t Bu)(SiMe t BuCH 2 ‐κ 2 ‐ N , C )}] ( 8 ) were identified by single‐crystal XRD (Scheme ).…”

“…[D 6 ]benzene was distilled from potassium, degassed by three freeze‐pump‐thaw cycles, and stored under argon. [UI 3 (THF) 4 ], UI 3 , UCl 4 , [ThCl 4 (THF) 3.5 ], 1 ,[10a] [{K(µ‐N**)} 2 ] ∞ ,[10a] [{K(µ‐N † ′)} 2 ] ∞ ,[10c] and [{K(N †† )} 2 ] ∞ [10b] were synthesized according to published procedures. 1 H, 13 C, and 29 Si NMR spectra were recorded with a Bruker DPX400 spectrometer operating at 400.2, 100.6, and 79.5 MHz respectively; chemical shifts are relative to TMS.…”

Insertion, protonolysis and photolysis reactivity of a thorium monoalkyl amidinate complex

“…Regardless, the alternative salt metathesis route using one equiv. of ThCl 4 (DME) 2 ( ref. 36 ) and 4.05 equiv.…”

Thorium–ligand multiple bonds via reductive deprotection of a trityl group

“…ThCl 4 (DME) 2 was synthesized according to the previously reported procedure. 71 All other reagents were purchased from commercial suppliers and used as received.…”