Synthesis of new alkyl and aryl σ-bonded uranium(IV) derivatives

Actinide Organometallic Chemistry

“…Thus, it was three decades after the Manhattan Project studies before the first thermally stable actinide alkyls, aryls, alkenyls, and alkynyls (collectively called hydrocarbyls) were synthesized (Eq. 13) (17,34,35). In …”

Synthesis and CO2 Insertion Chemistry of Uranium(IV) Mixed-Sandwich Alkyl and Hydride Complexes

“…As 11 and the "tuck-in" complex 6 are in equilibrium, H/D exchange into the Cp* ring Me groups can occur and was indeed observed. 2 H NMR spectroscopic studies on the reaction of the benzyl alkyl 3 and an excess of D 2 (ca. 3 equiv) followed over the course of 2 weeks showed increasingly intense and numerous resonances at shifts corresponding not only to deuterium in the Cp*-Me groups of 11, 6 ,and the U(III) complex [U III (COT TIPS2 )Cp*] (see Scheme 4) but also to the i Pr-CH 3 groups of all three species present.…”

“…Studies on the synthesis of uranium alkyl complexes were first reported in the early 1970s − and subsequently followed by the pioneering work of Andersen and Marks on organometallic uranium hydrides. , Since then, a range of uranium alkyl complexes have been reported featuring a variety of supporting ligand systems, both carbocylic and noncarbocylic in nature. Alkyl complexes utilizing the ubiquitous cyclopentadienyl (Cp) ligand and its substituted derivatives, − hard-donor ligands, − and bis(hydrotris(3,5-dimethylpyrazolyl)borate) ligands , have all been described, and the ability of U–C bonds to insert, in particular, CO 2 has been exemplified by the formation of a number of κ 2 -carboxylate complexes. ,− Uranium hydride complexes are still rare, and those reported feature substituted Cp ligands, − with the exception of Andersen’s bis(trimethylsilyl)amide hydride complex [UH(N{TMS} 2 ) 3 ] .…”

.sigma.-Bonded organic derivatives of f elements

“…The mass spectrum of the CpgUCeDs derivative revealed the loss of a CsHg ion which was given as further evidence that the mode of decomposition involved intramolecular proton abstraction. 34 This decomposition mechanism is further supported by the recently reported39 isolation and structural characterization of [Cp2Th(CsH4)]2 produced by the thermolysis of Cp3Th-rc-C4Hg. The molecular structure is that of a dimeric complex in which each thorium is ir ( 5) bonded to three cyclopentadienyl rings as well as bonded to one of the cyclopentadienyl rings of the other thorium.…”