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Small Molecule Activation at Uranium Coordination Complexes: Control of Reactivity Via Molecular Architecture

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Small Molecule Activation at Uranium Coordination Complexes: Control of Reactivity Via Molecular Architecture FEATURE ARTICLE www.rsc.org/chemcomm | ChemComm Small molecule activation at uranium coordination complexes: control of reactivity via molecular architecture Ingrid Castro-Rodrı´gueza and Karsten Meyer{*b Received (in Cambridge, UK) 27th September 2005, Accepted 15th November 2005 First published as an Advance Article on the web 24th January 2006 DOI: 10.1039/b513755c Electron-rich uranium coordination complexes display a pronounced reactivity toward small molecules. In this Feature article, the exciting chemistry of trivalent uranium ions coordinated to classic Werner-type ligand environments is reviewed. Three fundamentally important reactions of R the [(( ArO)3tacn)U]-system are presented that result in alkane coordination, CO/CO2 activation, and nitrogen atom-transfer chemistry. Introduction Historically, this is not surprising considering that until fairly recently, synthetic access to uranium(III) coordination From a synthetic chemist’s perspective, it is rather remarkable compounds was restricted due to lack of suitable starting that after fifty years of synthetic organometallic actinide i-Pr 3 materials. With the exception of homoleptic [( ArO)3U] and research, much is still unknown about the non-aqueous its derivatives,4 it was not until Clark and Sattelberger’s inorganic coordination chemistry of low-valent uranium.1,2 synthesis of the solvated trivalent [UI3L4] (L = THF and 5 aDepartment of Chemistry, University of California, Latimer Hall, DME) and the solvent-free [((Me3Si)2N)3U] complexes Berkeley, California, 94720, USA. E-mail: [email protected]; reported in a 1997 issue of Inorganic Synthesis that coordina- Tel: +1 510 642 2516 tion chemists finally had a synthetic protocol.6–9 This provided bDepartment of Chemistry and Biochemistry, University of California @ San Diego, 9500 Gilman Drive MC 0358, La Jolla, California, 92093- a convenient and highly reproducible entry into the exciting 0358, USA world of trivalent uranium chemistry. In the literature of the { Present address: Friedrich-Alexander-University Nuremberg- following years, there is an increasing number of articles Erlangen, Institute of Inorganic Chemistry, Egerlandstr. 1, 91058 Erlangen, Germany. E-mail: [email protected], Fax: reporting classical inorganic coordination complexes of +49 (0)9131 8527367, Tel: +49 (0)9131 8527360 uranium, which employ traditional inorganic ligands such as Ingrid Castro-Rodrı´guez was Karsten Meyer was born in born in 1977 in Rı´o Piedras, 1968 in Herne, Germany. In Puerto Rico. She received her May 1995, he received his Bachelor of Science degree in diploma in chemistry from chemistry at the University of the Ruhr-University Bochum. Puerto Rico (Rı´o Piedras He then began his graduate Campus) where she worked education under the direction with Professor Reginald of Professor Karl Wieghardt Morales on synthetic methods at the Max-Planck-Institute to isolate snake venoms. In for Bioinorganic Chemistry in fall 2000, Ingrid started her Mu¨lheim/Ruhr. Karsten’s studies in the Department of thesis work involved the synth- Chemistry and Biochemistry at esis and spectroscopic investi- the University of California, gation of transition metal San Diego, where she joined nitrido complexes. He received Ingrid Castro-Rodrı´guez Karsten Meyer Karsten’s laboratory in his doctoral degree in January January 2001. Ingrid’s research focused on the activation and 1998, which was awarded with distinction. Supported by a DFG functionalization of small molecules employing low-valent postdoctoral fellowship, he continued his education by joining the coordinatively unsaturated uranium complexes in sterically laboratory of Professor Christopher C. Cummins at the encumbering ligand environments. For her research accom- Massachusetts Institute of Technology (Cambridge, MA) where plishments she received UCSD’s Teddy Traylor award and a he developed his passion for uranium chemistry. In January 2001 Carl Storm fellowship from the Gordon Research Conference. he was appointed to the faculty of the University of California, After receiving her PhD in inorganic chemistry in summer 2005, San Diego and was named an Alfred P. Sloan Fellow in summer Ingrid was awarded a Glenn T. Seaborg postdoctoral fellowship 2004. Karsten has recently accepted a chair of inorganic and is currently working under the guidance of Professor Kenneth chemistry at the University of Erlangen-Nuremberg where he Raymond at the Lawrence Berkeley National Laboratory and will continue to pursue his research interests involving redox- University of California, Berkeley. active d-block and actinide metal complexes. The Meyer group specializes in manipulating complex reactivity by employing their understanding of molecular and electronic structure interplay. This journal is ß The Royal Society of Chemistry 2006 Chem. Commun., 2006, 1353–1368 | 1353 reactive [(Ar(Ad)N)3Mo] to form the hetero-bimetallic bridged 1 1 dinitrogen complex [(Ar(Ad)N)3Mo](m:g ,g -N2)[U(N(t- Bu)Ar)3] with an end-on coordinated N2 ligand. It was suggested that this complex forms via nucleophilic attack of an intermediate molybdenum–dinitrogen complex 16 [(Ar(Ad)N)3Mo(N2)] on the uranium(III) fragment. Another interesting reaction involving this class of com- pounds is the reaction of [(Ar(R)N)3U(I)] (R = C(CH3)3,Ar= 3,5-C6H3Me2) with toluene under strongly reducing condi- Chart 1 Selected chelating N-donor ligands for uranium coordina- tions, which leads to the formation of tion chemistry. 19,20 [{(Ar(R)N)2U}2(m-C7H8)] (Fig. 2). Following conventional electron-counting rules, the U centers in this dinuclear complex the chelating tris(2-pyridyl) and tris(2-pyrazinyl)methylamine are assigned the formal oxidation state of +II. As expected for (tpa and tpza),10,11 hydro-tris(pyrazolyl)borate (Tp2),12 tris- R 32 13 such a low-valent metal ion, this complex can be engaged in (amido)amine ( N3N ), macrocyclic calix[4]tetrapyrrole remarkable four-electron redox reactions with, e.g., azoben- tetraanion14 (Chart 1), as well as monodentate bis- zene and diphenyl disulfide compounds, yielding the (trimethylsilyl)amide and anilide (Ar(R)N2) systems.15 13 uranium(IV/IV) species [{(N(R)Ar)2U}2(m-NPh)2] and The electron-rich trivalent complexes [(N3N)U], 19 [{(N(R)Ar)2U(SPh)}2(m-SPh)2], respectively. However, the [(calix[4]pyrrole)U(dme)][K(dme)],14 [((Me Si) N) U]9 and 3 2 3 +II oxidation state has never been observed in U chemistry and [(N(R)Ar) U(THF)]16 exhibit an unusual and interesting 3 thus, it was suggested that in this complex strong d-back- reactivity towards the activation of small inert molecules such bonding reduces and activates the bridging arene. The uranium as the first example of dinitrogen activation by an actinide center’s ability to form strong covalent d-bonds in the context compound. The reactivity of these new, more classical, of arene binding therefore provides access to a previously coordination complexes exceeds, in some regards, that of the unknown divalent uranium synthon. thoroughly explored archetypal [(Cp) U]-system and its 3 More recently, pyrrole-based polyanions have emerged as derivatives. another class of versatile ligands for f-block metals. These The first example of dinitrogen fixation in actinide chemistry supporting ligands have proven to substantially increase the was reported by Scott and co-workers in 1998.17 The trivalent reactivity of their low-valent metal complexes. This is uranium complex [(N N)U] (obtained via reduction of 3 especially evident for the chelation of trivalent uranium by [(N N)UCl] and vacuum sublimation of the dinuclear pre- 3 the calix[4]tetrapyrrole tetraanion, which leads to binding and, cursor [{(N N)U} (m-Cl)], where N N = N(CH CH NSi- 3 2 3 2 2 most remarkably, cleavage of a dinitrogen ligand with (t-Bu)Me ) ) reversibly binds dinitrogen side-on forming the 2 3 formation of the unique m-nitrido mixed-valent UV/UIV complex [{(N N)U} (m:g2,g2-N )] (Fig. 1). This uranium 3 2 2 complex [{K(dme)(calix[4]tetrapyrrole)U} (m-NK) ][K(dme) ] complex also reacts with trimethylsilyl azide and trimethylsilyl 2 2 4 reported by Gambarotta in 2002.21 The highly reactive diazomethane to form the corresponding imido and hydrazido uranium(III) complex was also shown to participate in solvent complexes.13,18 deoxygenation and polysilanol depolymerization processes.21 Shortly after the first diuranium dinitrogen complex was The above-mentioned discoveries by Scott, Cummins, reported, Cummins and co-workers published the first stable heterodimetallic dinitrogen complex involving uranium.16 The Gambarotta and others have opened exciting new perspectives on actinide chemistry and evoked trust in the great potential mononuclear trivalent [(Ar(t-Bu)N)3U(THF)]?3THF complex, offered by trivalent uranium complexes for unprecedented which by itself is unreactive towards N2, was prepared employing the monodentate anilide ligand [Ar(t-Bu)N2]. chemical transformations. Despite this increased interest in new This trivalent uranium complex reacts with dinitrogen in the modes of uranium reactivity, the coordination chemistry of presence of the structurally very similar and exceedingly uranium complexes with coordinated macrocyclic polyamine ligands remained largely unexplored. With the exception of 2 2 Fig. 1 X-Ray crystal structure of [{(N3N)U}2(m:g ,g )] (CCDC code: Fig. 2 Solid-state molecular structure of [{(Ar(Ad)N)2U}2(m-C7H8)] PUKPEQ). (CCDC code: QIZRUM). 1354 | Chem. Commun., 2006, 1353–1368 This journal is ß The Royal Society of Chemistry 2006 our initial results in 200222 and an isolated report on a allow for control of complex reactivity via molecular uranium complex of a tris-amido derivatized triazacyclono- architecture. Herein it is shown that electron-rich uranium nane in 2003 (Chart 2, right),23 systematic studies on the complexes supported by an aryloxide-functionalized triazacy- molecular and electronic structure as well as the reactivity of clononane ligand provide a unique platform for enhanced uranium complexes supported by coordinated macrocyclic reactivity at a single uranium center.
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