Thorium aryloxides

The uranium(III) complexes Cp2UI2(THF)3 and Cp UI2(py)3 have been structurally characterized [393b]. The similar tribromide complex Cp ThBr3(THF)3 [111] provides a convenient entry into the chemistry of mono(pentamethylcyclopentadienyl) derivatives of thorium. Aryloxide and alkyl derivatives may be readily prepared by treatment of Cp RhBr3(THF)3 with potassium aryloxide or alkyl Grignard reagents, respectively [373], for example (5.58)-(5.60) ... 

Oxygen-Gontaining Organics. Neutral and anionic oxygen-containing organic molecules form complexes with thorium. Recent work has focused on alkoxides (72), aryloxides, and carboxylates however, complexes with alcohols, ethers, esters, ketones, aldehydes, ketoenolates, and carbamates are also well known. 

Aryloxide ligands, thorium, 24 770 Aryloxides, uranium complexation with, 25 436-437... 

A trimeric thorium hydride Th3H6(0 — 2, 6-/-Bu2C6H3)6, which represents a rare example of an early-metal hydrido complex supported exclusively by aryloxide ligation, was synthesized according to reaction (5.69), and its structure is shown in 985 [352] ... 

Lewis base adducts of thorium(IV) and uranium(IV) aryloxides are readily prepared. Initial reports of phenoxide compounds of uranium(IV) describe NH3 derivatives from the reaction of UCI4 or UOCI2 with appropriate phenols in the presence of ammonia " (see Equations (15) to (17)) ... 

The metals thorium and uranium (as with the chemistry in general of these elements) dominate actinide aryloxide chemistry. Synthetic strategies normally focus on the halides reacting with group 1 metal aryloxides or reaction of metal amides with phenols. An important piece of early work was the demonstrated interconversion of eight-coordinate [UMe4(dmpe)2] and [M(OPh)4(dmpe)2] (M = Th, U Table 6.20) by addition of phenol or MeLi to each substrate respectively. The reaction of the cyclometallated... 

The only N2 related thorium chemistry concerns the noncatalytic activation of N2 to form an NH2-group in a compHcated reaction sequence (Scheme 85). On addition of KCioHg to the Th aryloxide species 328 under an N2 atmosphere the thorium amido complex 330 is slowly formed by N2 cleavage and proton abstraction (presumably from the solvent).Nevertheless, when the reduction is carried out with an excess of KCioHg, compound 329 was isolated that acts as a Th(0) synthon. 

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