448186-93-4

Upstream product

• 983-79-9 benzophenone azine 
• 874285-96-8 [uranium(III)(1,2,3,4,5-pentamethylcyclopentadienide)2(2,2'-bipyridine)] 
• 67605-92-9 dimethylbis(η5-pentamethylcyclopentadienyl)uranium 
• 67506-89-2 bis(pentamethylcyclopentadienyl)dichlorouranium(IV) 
• 100-47-0 benzonitrile 

Relevant academic research and scientific papers

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

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

The first f-element ketimido complex: Synthesis and characterization of (C5Me5)2U(-N=CPh2)2

The first example of an f-element ketimido complex has been prepared. Complex 2 is surprisingly unreactive and displays unusual electronic properties. The physical properties and chemical stability of this complex suggest higher U - N bond order due to si

Small-molecule activation mediated by a uranium bipyridyl metallocene

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).

(η5-C5Me5)2U(=P-2,4,6-tBu3C6H2)(OPMe3) Revisited-its intrinsic reactivity toward small organic molecules

The Lewis base stabilized uranium phosphinidene (η5C5Me5)2U(=P-2,4,6-tBu3C6H2)(OPMe3) (2), which was derived from (η5-C5Me5)2U(Cl)Me (1) and 2,4,6-(Me3C)3C6H2PHK in toluene in the presence of Me3PO, was originally reported in 1996, but since then its reactivity toward small organic molecules has not been extensively explored. This contribution closes this gap, and divergent reactivity patterns are established in the reaction of complex 2 toward (small) organic substrates. For example, complex 2 may release the phosphinidene moiety (2,4,6-tBu3C6H2P:) and therefore may act as a source of a (η5C5Me5)2UII fragment in the presence of Ph2S2, Ph2Se2, bipy, ketazine (Ph2C=N)2, and conjugated alkynes RC=CC=CR, forming the disulfido compound (η5-C5Me5)2U(SPh)2 (5), diselenido compound (η5-C5Me5)2U(SePh)2 (6), bipy compound (η5-C5Me5)2U(bipy) (8), diiminato compound (η5-C5Me5)2U(N=CPh2)2 (9) and the metallacyclopentatrienes (η5-C5Me5)2U[η4-C4(R)2] (R = Ph (10), Me3Si (11)), respectively. Furthermore, compound 2 may also straightforwardly react with terminal alkynes and a variety of heterounsaturated (organic) molecules such as CS2, isothiocyanates, imines, diazenes, carbodiimides, nitriles, isonitriles, and organic azides. For instance, on treatment with phenylacetylene (PhC=CH) the dialkynyl uranium complex (η5-C5Me5)2U(C2Ph)2(OPMe3) (12) is formed, whereas CS2 and PhNCS furnish the carbodithioates (η5-C5Me5)2U[SC(=P-2,4,6-tBu3C6H2)S](OPMe3) (13) and (η5-C5Me5)2U[SC(=NPh)S](OPMe3) (14), respectively. In the reaction of the secondary aldimine PhCH= NPh or the diazene PhN=NPh and 2 the uranium(IV) imido complex (η5-C5Me5)2U(=NPh)(OPMe3) (15) is isolated, which is in contrast to its reactivity with the primary ketimine 9-(C12H8)C=NH and the carbodiimides (RN=)2C, yielding the diiminato uranium(VI) complex (η5-C5Me5)2U[N=C(C12H8)]2 (16) and the four-membered uranaheterocycles (η5-C5Me5)2U[N(R)C(=P-2,4,6-tBu3C6H2)N(R)] (R = C6H11 (17), iPr (18)), respectively. Furthermore, treatment of 2 with nitriles RCN affords the imido uranium(IV) complexes (η5-C5Me5)2U[=NC(=P-2,4,6-tBu3C6H2)R](OPMe3) (R = C6H11 (19), Me3C (20)), whereas isonitriles RNC furnish the metallaaziridines (η5-C5Me5)2U[C(=P-2,4,6-tBu3C6H2)N(R)](OPMe3) (R = C6H11 (21), 2,6-Me2Ph (22)). However, in the reaction with organic azides RCN3, complex 2 yields the imido uranium(IV) complexes (η5-C5Me5)2U(= NR)(OPMe3) (R = Ph3C (23), p-tolyl (24)) as a result of 3,3-Me2-5,7-tBu2C8H5P (7) formation and N2 release. The new compounds 12-24 were characterized by various spectroscopic techniques, including single-crystal X-ray diffraction analyses. Furthermore, with complex 2 in hand a comparison between the reactivity of uranium phosphinidenes differing in the steric bulk of its cyclopentadienyl ligands and the effects of a Lewis base (OPMe3) adduct was undertaken.

Thorium(IV) and uranium(IV) ketimide complexes prepared by nitrile insertion into actinide-alkyl and -aryl bonds

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.