448186-93-4Relevant articles and documents
Tuning the Oxidation State, Nuclearity, and Chemistry of Uranium Hydrides with Phenylsilane and Temperature: The Case of the Classic Uranium(III) Hydride Complex [(C5Me5)2U(μ-H)]2
Pagano, Justin K.,Dorhout, Jacquelyn M.,Czerwinski, Kenneth R.,Morris, David E.,Scott, Brian L.,Waterman, Rory,Kiplinger, Jaqueline L.
, p. 617 - 620 (2016)
This work demonstrates that the oxidation state and chemistry of uranium hydrides can be tuned with temperature and the stoichiometry of phenylsilane. The trivalent uranium hydride [(C5Me5)2U-H]x (5) was found t
Small-molecule activation mediated by a uranium bipyridyl metallocene
Zhang, Lei,Zhang, Congcong,Hou, Guohua,Zi, Guofu,Walter, Marc D.
, p. 1179 - 1187 (2017)
Addition of potassium graphite (KC8) to a solution of (η5-C5Me5)2UCl2 (1) and 2,2'-bipyridine (bipy) gives the uranium bipyridyl metallocene (η5-C5Me5)2U(bipy) (2) in good yield. In complex 2 a bipy radical anion is coordinated to a U(III) atom, and it is therefore an ideal starting material for small-molecule activation: e.g., it serves as a synthetic equivalent for the (η5-C5Me5)2UII fragment on treatment with conjugated alkynes and a variety of heterounsaturated molecules such as imines, carbodiimide, organic azides, hydrazine, and azo derivatives. Alternatively, it may also react with aldehydes, ketones, nitriles, and α,β-unsaturated reagents such as p-ClPhCHO, (CH2)5CO, PhCN, and methyl methacrylate (MMA), forming the C-C bond coupling products (η5 - C5Me5)2U[(bipy)(p-ClPhCHO)] (10), (η5-C5Me5)2U[(bipy){(CH2)5CO}] (11), (η5-C5Me5)2U[(bipy)(PhCN)] (12), (η5-C5Me5)2U[(bipy){CH2=C(Me)CO(OMe)] (13a), and [(η5-C5Me5)2U{OC(OMe)=C(Me)CH2-3-bipy}]2 (13b), respectively, in quantitative conversion. Furthermore, addition of CuI to complex 2 induces a single-electron-transfer process to form the uranium(III) iodide complex (η5-C5Me5)2U(I)(bipy) (14).
Thorium(IV) and uranium(IV) ketimide complexes prepared by nitrile insertion into actinide-alkyl and -aryl bonds
Jantunen, Kimberly C.,Burns, Carol J.,Castro-Rodriguez, Ingrid,Da Re, Ryan E.,Golden, Jeffery T.,Morris, David E.,Scott, Brian L.,Taw, Felicia L.,Kiplinger, Jaqueline L.
, p. 4682 - 4692 (2008/10/09)
Migratory insertion of benzonitrile into both An-C bonds of the bis(alkyl) and bis(aryl) complexes (C5Me5)2AnR2 yields the actinide ketimido complexes (C5Me5) 2An[-N=C(Ph)(R)]2 (where An = Th, R = Ph, CH 2Ph, CH3; An = U, R = CH2Ph, CH3) and provides a versatile method for the construction of electronically and sterically diverse ketimide ligands. The Th(IV) compounds represent the first examples of thorium ketimide complexes. The uranium complexes are surprisingly unreactive, and both the uranium and thorium bis(ketimido) complexes display unusual electronic structure properties. The combined chemical and physical properties of these complexes suggest a higher An-N bond order due to significant ligand-to-metal π-bonding in the actinide ketimido interactions and indicate that the f-electrons in mid-valent organouranium complexes might be far more involved in chemical bonding and reactivity than previously thought. We also report herein the structures of the known thorium and uranium complexes (C5Me5)2Th(CH2Ph)2, (C5Me5)2ThMe2, (C5Me 5)2U(CH2Ph)2, and (C 5Me5)2UMe2.
