Uranium(iii) and thorium(iv) alkyl complexes as potential starting materials.

The synthesis and characterisation of a rare U(iii) alkyl complex, U[η4-Me2NC(H)C6H5]3, using the dimethylbenzylamine (DMBA) ligand has been accomplished. While attempting to prepare the U(iv) compound, reduction to the U(iii) complex occurred. In the analogous Th(iv) system, C-H bond activation of a methyl group of one dimethylamine was observed yielding Th[η4-Me2NC(H)C6H5]2[η5-(CH2)MeNC(H)C6H5] with a dianionic DMBA ligand. The utility of these complexes as starting materials has been analyzed using a bulky dithiocarboxylate ligand to yield tetravalent actinide species.

[1]  F. Ortu,et al.  New vistas in the molecular chemistry of thorium: low oxidation state complexes. , 2016, Dalton transactions.

[2]  Guang Wu,et al.  Synthesis and Reactivity of a U(IV) Dibenzyne Complex , 2016 .

[3]  Guang Wu,et al.  Synthesis, structure and bonding of hexaphenyl thorium(IV): observation of a non-octahedral structure. , 2016, Chemical communications.

[4]  A. Kerridge,et al.  Dithio- and Diselenophosphinate Thorium(IV) and Uranium(IV) Complexes: Molecular and Electronic Structures, Spectroscopy, and Transmetalation Reactivity. , 2015, Inorganic chemistry.

[5]  B. Scott,et al.  Coordination chemistry of 2,2'-biphenylenedithiophosphinate and diphenyldithiophosphinate with U, Np, and Pu. , 2015, Dalton transactions.

[6]  Sara A. Johnson,et al.  New Benzylpotassium Reagents and Their Utility for the Synthesis of Homoleptic Uranium(IV) Benzyl Derivatives , 2015 .

[7]  J. Ziller,et al.  Actinide Metallocene Hydride Chemistry: C–H Activation in Tetramethylcyclopentadienyl Ligands to Form [μ-η5-C5Me3H(CH2)-κC]2– Tuck-over Ligands in a Tetrathorium Octahydride Complex , 2013 .

[8]  Guang Wu,et al.  Comparison of the reactivity of 2-Li-C6H4CH2NMe2 with MCl4 (M=Th, U): isolation of a thorium aryl complex or a uranium benzyne complex. , 2013, Angewandte Chemie.

[9]  Guang Wu,et al.  In pursuit of homoleptic actinide alkyl complexes. , 2013, Inorganic chemistry.

[10]  J. van Slageren,et al.  The inherent single-molecule magnet character of trivalent uranium. , 2013, Angewandte Chemie.

[11]  R. Baker,et al.  The coordination and organometallic chemistry of UI3 and U{N(SiMe3)2}3: Synthetic reagents par excellence , 2012 .

[12]  P. Fanwick,et al.  Carbon-carbon reductive elimination from homoleptic uranium(IV) alkyls induced by redox-active ligands. , 2012, Journal of the American Chemical Society.

[13]  Katie R. Meihaus,et al.  Dilution-induced slow magnetic relaxation and anomalous hysteresis in trigonal prismatic dysprosium(III) and uranium(III) complexes. , 2011, Inorganic chemistry.

[14]  Joseph A. R. Schmidt,et al.  Synthesis and Reactivity of Homoleptic α-Metalated N,N-Dimethylbenzylamine Rare-Earth-Metal Complexes , 2011 .

[15]  Guang Wu,et al.  High-valent uranium alkyls: evidence for the formation of U(VI)(CH2SiMe3)6. , 2011, Journal of the American Chemical Society.

[16]  P. Fanwick,et al.  Functionalization of carbon dioxide and carbon disulfide using a stable uranium(III) alkyl complex. , 2011, Journal of the American Chemical Society.

[17]  J. Ziller,et al.  Synthesis of a thorium tuck-in complex, [(eta(5):eta(1)-C(5)Me(4)CH(2))(eta(5)-C(5)Me(5))Th{iPrNC(Me)NiPr}], by C-H bond activation initiated by (C(5)Me(5))(-). , 2009, Chemistry.

[18]  B. Melot,et al.  Homoleptic uranium(IV) alkyl complexes: synthesis and characterization. , 2009, Journal of the American Chemical Society.

[19]  J. Long,et al.  Slow magnetic relaxation in a trigonal prismatic uranium(III) complex. , 2009, Journal of the American Chemical Society.

[20]  M. Ephritikhine,et al.  Homoleptic tris(dithiolene) and tetrakis(dithiolene) complexes of uranium(IV). , 2005, Inorganic chemistry.

[21]  B. Scott,et al.  Thorium(IV) and Uranium(IV) Ketimide Complexes Prepared by Nitrile Insertion into Actinide−Alkyl and −Aryl Bonds , 2004 .

[22]  T. Marks,et al.  Electronic Structure and Photoelectron Spectroscopy of the Monomeric Uranium(III) Alkyl [η5-(CH3)5C5]2UCH[Si(CH3)3]2†,‡ , 1996 .

[23]  D. L. Clark,et al.  Synthesis, characterization, and x-ray structure of the uranium thiolate complex U(S-2,6-Me2C6H3)[N(SiMe3)2]3 , 1993 .

[24]  O. P. Anderson,et al.  Synthesis and structure of two organozirconocenes with .alpha. nitrogen substituents , 1992 .

[25]  C. Burns,et al.  First example of a neutral homoleptic uranium alkyl. Synthesis, properties, and structure of U[CH(SiMe3)2]3 , 1989 .

[26]  R. Andersen,et al.  Preparation of tetraalkyl phosphine complexes of the f-block metals. Crystal structure of Th(CH2Ph)4(Me2PCH2CH2PMe2) and U(CH2Ph)3Me(Me2PCH2CH2PMe2) , 1984 .

[27]  J. Zellweger,et al.  Dithiophosphinate complexes of the actinides. Part 1. Preparation and characterisation of complexes of thorium(IV) and the crystal structures of [Th(S2PR2)4], R = Me or C6H11 , 1981 .

[28]  R. Andersen Tris((hexamethyldisilyl)amido)uranium(III): preparation and coordination chemistry , 1979 .

[29]  C. Day,et al.  Pentamethylcyclopentadienyl Organoactinides. Trivalent Uranium Organometallic Chemistry and the Unusual Structure of Bis(pentamethylcyclopentadienyl)uranium Monochloride , 1979 .

[30]  J. Sebastian,et al.  Direct observation of metalated N,N-dimethylbenzylamines by ft NMR spectroscopy , 1978 .

[31]  R. D. Shannon Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides , 1976 .

[32]  D. Brown,et al.  Structure of thorium(IV) tetrakis-(NN-diethyldithiocarbamate) , 1970 .