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Carbene Imido Oxo Complex** Erli Lu, Oliver J

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Carbene Imido Oxo Complex** Erli Lu, Oliver J Angewandte. Zuschriften DOI: 10.1002/ange.201403892 Metal–Ligand Multiple Bonds Synthesis, Characterization, and Reactivity of a Uranium(VI) Carbene Imido Oxo Complex** Erli Lu, Oliver J. Cooper, Jonathan McMaster, Floriana Tuna, Eric J. L. McInnes, William Lewis, Alexander J. Blake, and Stephen T. Liddle* Abstract: We report the uranium(VI) carbene imido oxo limited to homoleptic systems, such as uranium trioxide and TMS TMS [2c] complex [U(BIPM )(NMes)(O)(DMAP)2](5, BIPM = triscarbenes, or heteroleptic UL2L’ systems with a maxi- C(PPh2NSiMe3)2 ; Mes = 2,4,6-Me3C6H2 ; DMAP = 4-(dime- mum of two different types of multiply bonded ligands, such thylamino)pyridine) which exhibits the unprecedented as a uranyl–carbene.[2f] Remarkably, no heteroleptic ULL’L’’ arrangement of three formal multiply bonded ligands to one uranium complexes containing three different multiple bond metal center where the coordinated heteroatoms derive from linkages to uranium have ever been reported. Furthermore, different element groups. This complex was prepared by even for d-block complexes where metal–ligand (ML) incorporation of carbene, imido, and then oxo groups at the multiple bonding is more favorable, homoleptic combina- uranium center by salt elimination, protonolysis, and two- tions are so dominant that there are no examples of electron oxidation, respectively. The oxo and imido groups MLL’L’’ multiply bonded complexes containing heteroatoms adopt axial positions in a T-shaped motif with respect to the from different element groups; the only example of a carbene, which is consistent with an inverse trans-influence. MLL’L’’ complex from hundreds of examples of ML multi- Complex 5 reacts with tert-butylisocyanate at the imido rather ple bond complexes is the all-chalcogen complex [W- [12] than carbene group to afford the uranyl(VI) carbene complex (C5Me5)(O)(S)(Se)][PPh4], reported over a decade ago. TMS [U(BIPM )(O)2(DMAP)2](6). This paucity may reflect the difficulties of constructing different covalent ML multiple bonds at a metal center There is burgeoning interest in covalent uranium–ligand whilst avoiding decomposition of previously installed (UL) multiple bonding because of the ongoing debate multiple bonds. Although MLL’L’’ complexes utilizing heter- regarding the level and nature of covalency that these bonds oatoms from different element groups are yet to be reported, may exhibit.[1] Uranium UL compounds containing covalent their synthesis would establish new synthetic strategies, give terminal monocarbene, -imido, -nitride, and -chalcogenide structure–bonding insights, and allow competitive reactivity [2–5] linkages are well known. Homoleptic UL2 compounds are studies to be investigated. also well represented; in addition to a modest range of Herein, we describe the synthesis of a uranium(VI) uranium biscarbene and bisimido complexes,[2b,d,6] the bisoxo carbene imido oxo complex, which is the first example of uranyl unit accounts for more than 50% of all structurally a metal complex to exhibit formal covalent multiple-bond characterized uranium complexes.[7] Recently, progress has interactions to three different ligands with heteroatoms from been made preparing heteroleptic ULL’ complexes with different element groups, and we describe its structure, carbene–oxo,[2k] imido–oxo,[8] nitrido–oxo,[9] and heavier bonding, and preliminary reactivity. [10] TMS chalcogen–oxo compounds. Although both rare and chal- The starting material [U(BIPM )(Cl)(m-Cl)2Li(THF)2] TMS [2j] lenging to prepare, these compounds are of interest with (1, BIPM = C(PPh2NSiMe3)2) was treated with two respect to the inverse trans-influence (ITI),[11] where strong equivalents of benzyl potassium to afford, after workup and donor ligands adopt trans geometries in contrast to d-block recrystallization, the brown uranium(IV) carbene dialkyl TMS [13] analogues that tend to adopt cis geometries. Concerning complex [U(BIPM )(CH2Ph)2](2) in 72% yield. Al- three-ligand multiple-bond linkages to uranium, examples are though a number of uranium carbene derivatives have now been reported, dialkyls were unknown.[2] Treatment of 2 with [13] [*] Dr. E. Lu, Dr. O. J. Cooper, Dr. J. McMaster, Dr. W. Lewis, mesitylamine, Scheme 1, gave the uranium(IV) carbene TMS Prof. A. J. Blake, Prof. S. T. Liddle imido complex [{U(BIPM )(m-NMes)}2](3) as brown School of Chemistry, University of Nottingham crystals in 92% yield. We tested the oxidation of 3 with University Park, Nottingham, NG7 2RD (UK) common oxygen-atom-transfer reagents and found that whilst E-mail: [email protected] morpholine N-oxide, pyridine-N-oxide, and trimethylamine- Dr. F. Tuna, Prof. E. J. L. McInnes N-oxide all gave intractable products, tetramethylpiperidine- School of Chemistry and Photon Science Institute N-oxide (TEMPO) effected clean oxidation to afford the University of Manchester, Oxford Road black uranium(VI) carbene imido oxo complex [{U- Manchester, M13 9PL (UK) (BIPMTMS)(NMes)(m-O)} ](4) as a crystalline product in [**] We thank the Royal Society, Marie Curie International Incoming 2 Fellowship Scheme, European Research Council, Engineering and 57% yield. Complex 4 was treated with two equivalents of Physical Sciences Research Council, University of Nottingham, and DMAP to give the uranium(VI) carbene imido oxo complex TMS National Nuclear Laboratories for generous support of this work. [U(BIPM )(NMes)(O)(DMAP)2](5) as black crystals. Supporting information for this article is available on the WWW Complex 5 can also be prepared in 49% yield from a one- under http://dx.doi.org/10.1002/anie.201403892. pot reaction of 3 with TEMPO and two equivalents of DMAP. 6814 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Angew. Chem. 2014, 126, 6814 –6818 Angewandte Chemie Scheme 1. Synthesis of compounds 3–5. (Compound 2 was prepared from 1 and KCH2C6H5). The characterization data for compounds 2–5 are consis- tent with their formulations. The 31P NMR spectrum of 5 has a resonance signal at d = À22 ppm, shifted from d = À35 ppm for 4. Despite exhaustive attempts we could not locate the carbene resonances in the 13C NMR spectra of 4 or 5 in the range d = À200 to + 1000 ppm and no folded-in resonances could be detected; 2D 13C-31P NMR experiments showed only one cross-peak for the P-phenyl ipso carbon atoms. In contrast, in a cerium(IV) BIPMTMS carbene complex, this method easily located the carbene resonance at d =+ 325 ppm.[14] The FTIR spectra of 4 and 5 exhibit strong bands at 837 and 900 cmÀ1, which we attribute to bridging and terminal oxo groups, respectively. The UV/Vis electronic absorption spectra of 2–5 are dominated by LMCT (ligand-to- metal charge transfer) absorptions that tail in from the UV region to the visible and the NIR regions are generally featureless (4 and 5) or exhibit very weak f!f absorptions (2 and 3). The profile of the experimental UV/Vis absorption spectrum of 5 is reproduced well by SAOP/ZORA/TZP TD- DFT calculations, with the absorptions in the l = 400–750 nm range arising principally from LMCT transitions involving the carbene and imido lone pairs to vacant uranium 5forbitals.[13] The uranium(IV) formulations of 2 and 3 were confirmed by [13] SQUID magnetometry. The magnetic moment of 2 is 2.6 mB at 298 K and this falls to 0.8 mB at 1.8 K. For 3, the magnetic Figure 1. Single-crystal X-ray structures of a) [{U(BIPMTMS)(NMes)(m- moment at 298 K is 3.4 mB (2.4 mB per uranium center) and this TMS O)}2](4), b) [U(BIPM )(NMes)(O)(DMAP)2](5), and c) [U- falls to 1.04 mB at 1.8 K (0.7 mB per uranium center). The TMS (BIPM )(O)2(DMAP)2](6). Displacement ellipsoids set at 40% magnetic moments of 2 and 3 both tend to zero and are probability. Hydrogen atoms, any lattice solvent, and minor disorder consistent with uranium(IV) which is a magnetic singlet at components are omitted for clarity. Selected bond lengths []: 4: U1– low temperature. We find no evidence of magnetic coupling C1 2.408(3), U1–N1 2.408(3), U1–N2 2.374(3), U1–N3 1.943(3), U1– between the two uranium(IV) centers in 3, but coupling O1 1.953(2), U1–O1A 2.337(2); 5: U1–C1 2.400(3), U1–N1 2.554(2), between uranium(IV) centers is rarely observed.[15] U1–N2 2.577(2), U1–N3 1.921(2), U1–N4 2.592(2), U1–N5 2.611(2), U1–O1 1.814(2); 6: U1–C1 2.383(3), U1–N1 2.606(2), U1–N2 Compounds 2–5 have been characterized by single-crystal [13] 2.600(2), U1–N3 2.564(3), U1–N4 2.594(3), U1–O1 1.794(2), U1–O2 X-ray diffraction. The structure of 5 (Figure 1b) confirms 1.785(2). the monomeric formulation. In this structure, the uranium center is coordinated to terminal carbene, imido, and oxo motif with respect to the carbene. However, unlike uranyl groups with two coordinated molecules of DMAP completing which typically exhibits O-U-O angles of more than 1728, the a pentagonal-bipyramidal coordination sphere. Notably, the N-U-O angle is distorted significantly from linearity at oxo and imido groups adopt axial positions in a T-shaped 167.14(9)8. This angle is close to the angle of 1618 measured Angew. Chem. 2014, 126, 6814 –6818 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.angewandte.de 6815 Angewandte. Zuschriften in gas-phase UO3 which also adopts a distorted T-shaped carbene, imido, and oxo donors. However, these orbitals are geometry.[16] The N-U-O angle in 5 is slightly closer to extensively delocalized across each donor group and the linearity than in 4 (160.49(11)8; Figure 1a), but this most uranium center, precluding an assessment of ITI effects; this likely reflects the increase in coordination number at uranium contrasts to calculations on 6 (see below) where the orbitals in 5 (seven-coordinate) compared to 4 (six-coordinate).
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