Siloxides as supporting ligands in uranium(III)-mediated small-molecule activation.

Siloxides can support U! in the reduction of small molecules with uranium complexes. The treatment of [UN(SiMe3)23] with HOSi(OtBu)3 (3 equiv) yielded a novel homoleptic uranium(III) siloxide complex 1, which acted as a two-electron reducing agent toward CS 2 and CO2 (see scheme). Complex 1 also reduced toluene to afford a diuranium inverted-sandwich complex. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

[1]  C. Mealli,et al.  A New Bridging Mode of Carbon Disulfide in a Dinuclear Cobalt(I) Complex , 1979 .

[2]  W. Evans,et al.  Expanding the chemistry of U3+ reducing agents , 2006 .

[3]  Guang Wu,et al.  Synthesis of a nitrido-substituted analogue of the uranyl ion, [N=U=O]+. , 2010, Journal of the American Chemical Society.

[4]  K. Meyer,et al.  Small molecule activation at uranium coordination complexes: control of reactivity via molecular architecture. , 2006, Chemical communications.

[5]  P. Arnold,et al.  Small molecule activation by uranium tris(aryloxides): experimental and computational studies of binding of N2, coupling of CO, and deoxygenation insertion of CO2 under ambient conditions. , 2011, Journal of the American Chemical Society.

[6]  J. Ziller,et al.  Insights into the mechanism of reaction of [(C5Me5)2Sm(II)(thf)2] with CO2 and COS by DFT studies. , 2012, Chemistry.

[7]  P. Arnold,et al.  Arene-Bridged Diuranium Complexes: Inverted Sandwiches Supported by δ Backbonding , 2000 .

[8]  W. Duax,et al.  Crystal Structure and Molecular Motion of Solid Carbon Disulfide , 1968 .

[9]  P. Arnold.  Uranium-mediated activation of small molecules. , 2011, Chemical communications.

[10]  C. Cummins,et al.  Towards uranium catalysts , 2008, Nature.

[11]  K. Meyer,et al.  Uranium-mediated carbon dioxide activation and functionalization , 2012 .

[12]  M. Ephritikhine,et al.  Arene uranium borohydrides: synthesis and crystal structure of η-C6Me6)U(BH4)3 , 1989 .

[13]  P. Arnold,et al.  Spontaneous reduction and C-H borylation of arenes mediated by uranium(III) disproportionation. , 2012, Nature chemistry.

[14]  J. Ziller,et al.  Molecular Octa-Uranium Rings with Alternating Nitride and Azide Bridges , 2005, Science.

[15]  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.

[16]  Peter G. Jones,et al.  Catalytic metathesis of conjugated diynes. , 2012, Angewandte Chemie.

[17]  P. Arnold,et al.  Carbon monoxide coupling and functionalisation at a simple uranium coordination complex , 2011 .

[18]  C. Krempner.  Role of Siloxides in Transition Metal Chemistry and Homogeneous Catalysis , 2011 .

[19]  D. L. Clark,et al.  New developments in actinide alkoxide chemistry , 1992 .

[20]  P. Hitchcock,et al.  Reductive disproportionation of carbon dioxide to carbonate and squarate products using a mixed-sandwich U(III) complex. , 2009, Chemical communications.

[21]  C. Burns,et al.  Uranium alkoxide chemistry. 1. Synthesis and the novel dimeric structure of the first homoleptic uranium(III) aryloxide complex , 1988 .

[22]  R. Andersen,et al.  Chemistry of Trivalent Uranium Metallocenes: Electron-Transfer Reactions with Carbon Disulfide. Formation of [(RC5H4)3U]2[μ= η1, η2-CS2] , 1986 .

[23]  S. Gambarotta,et al.  A highly reactive uranium complex supported by the calix[4]tetrapyrrole tetraanion affording dinitrogen cleavage, solvent deoxygenation, and polysilanol depolymerization. , 2002, Angewandte Chemie.

[24]  F. Heinemann,et al.  Formation of a uranium trithiocarbonate complex via the nucleophilic addition of a sulfide-bridged uranium complex to CS2. , 2012, Inorganic chemistry.

[25]  J. Ziller,et al.  A comparative synthetic and structural study of triphenylmethoxide and triphenylsiloxide complexes of the early lanthanides, including x-ray crystal structures of La2(OCPh3)6 and Ce2(OSiPh3)6 , 1991 .

[26]  K. Meyer,et al.  Carbon dioxide reduction and carbon monoxide activation employing a reactive uranium(III) complex. , 2005, Journal of the American Chemical Society.

[27]  I. D. Brown,et al.  Bond‐valence parameters obtained from a systematic analysis of the Inorganic Crystal Structure Database , 1985 .

[28]  A. J. Blake,et al.  A delocalized arene-bridged diuranium single-molecule magnet. , 2011, Nature chemistry.

[29]  N. Lewis,et al.  Powering the planet: Chemical challenges in solar energy utilization , 2006, Proceedings of the National Academy of Sciences.

[30]  R. Schrock,et al.  Surface versus molecular siloxy ligands in well-defined olefin metathesis catalysts: [{(RO)3SiO}Mo(=NAr)(=CHtBu)(CH2tBu)]. , 2006, Angewandte Chemie.

[31]  L. Maron,et al.  Facile conversion of CO/H2 into methoxide at a uranium(III) center. , 2011, Angewandte Chemie.

[32]  A. J. Blake,et al.  A formal high oxidation state inverse-sandwich diuranium complex: a new route to f-block-metal bonds. , 2011, Angewandte Chemie.

[33]  L. Maron,et al.  Carbonate Formation from CO2 via Oxo versus Oxalate Pathway: Theoretical Investigations into the Mechanism of Uranium-Mediated Carbonate Formation† , 2010 .

[34]  L. Maron,et al.  Insight into the reaction mechanisms of (MeC5H4)3U with isoelectronic heteroallenes CS2, COS, PhN3, and PhNCO by DFT studies: a unique pathway that involves bimetallic complexes. , 2012, Chemistry.

[35]  Marisa J. Monreal,et al.  Molecular quadrangle formation from a diuranium μ-η6,η6-toluene complex. , 2011, Chemical Communications.

[36]  C. Anthon,et al.  Influence of steric pressure on the activation of carbon dioxide and related small molecules by uranium coordination complexes. , 2009, Dalton transactions.

[37]  J. Ziller,et al.  Structure, reactivity, and density functional theory analysis of the six-electron reductant, [(C5Me5)2U]2(mu-eta6:eta6-C6H6), synthesized via a new mode of (C5Me5)3M reactivity. , 2004, Journal of the American Chemical Society.

[38]  S. Bott,et al.  A convenient entry into trivalent actinide chemistry : synthesis and characterization of AnI3(THF)4 and an[N(SiMe3)2]3 (an = U, Np, Pu) , 1994 .

[39]  Saeed I. Khan,et al.  In situ generation of uranium alkyl complexes. , 2010, Chemical communications.

[40]  A. J. Blake,et al.  Homologation and functionalization of carbon monoxide by a recyclable uranium complex , 2012, Proceedings of the National Academy of Sciences.

[41]  Christopher C. Cummins,et al.  Heterodinuclear Uranium/Molybdenum Dinitrogen Complexes , 1998 .

[42]  M. Aresta,et al.  Utilisation of CO2 as a chemical feedstock: opportunities and challenges. , 2007, Dalton transactions.

[43]  L. Zakharov,et al.  A Linear, O-Coordinated η1-CO2 Bound to Uranium , 2004, Science.

[44]  C. Bianchini,et al.  Eine Carbondisulfidbrücke neuen Typs in einem zweikernigen Cobalt(I)‐Komplex , 1979 .

[45]  C. Cummins,et al.  μ-η6,η6-Arene-bridged diuranium hexakisketimide complexes isolable in two states of charge. , 2012, Inorganic chemistry.

[46]  P. T. Wolczanski.  Chemistry of electrophilic metal centres coordinated by silox (tBu3SiO), tritox (tBu3CO) and related binfunctional ligands , 1995 .

[47]  Z. Hou,et al.  A novel binuclear samarium(II) complex bearing mixed cyclopentadienide/siloxide ligands: [(C5Me5)Sm{μ-OSi(OtBu)3}3Sm]. Synthesis, structure, electron-transfer, and unusual metal-coordination reactions , 2004 .

[48]  A. Fürstner,et al.  Molybdenum nitride complexes with Ph3SiO ligands are exceedingly practical and tolerant precatalysts for alkyne metathesis and efficient nitrogen transfer agents. , 2009, Journal of the American Chemical Society.

[49]  J. Huffman,et al.  Early actinide alkoxide chemistry. Synthesis, characterization, and molecular structures of Th(IV) and U(IV) aryloxide complexes , 1992 .

[50]  F. Heinemann,et al.  Insights into the mechanism of carbonate formation through reductive cleavage of carbon dioxide with low-valent uranium centers. , 2010, Chemical communications.