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Activation of Carbon Suboxide (C3O2) by U(III) to Form a Cyclobutane­1,3­Dione Ring

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Activation of Carbon Suboxide (C3O2) by U(III) to Form a Cyclobutane­1,3­Dione Ring Activation of carbon suboxide (C3O2) by U(III) to form a cyclobutane-1,3-dione Ring. Article (Accepted Version) Tsoureas, Nikolaos and Cloke, Frederick Geoffrey (2018) Activation of carbon suboxide (C3O2) by U(III) to form a cyclobutane-1,3-dione Ring. Chemical Communications, 54 (64). pp. 8830- 8833. ISSN 1359-7345 This version is available from Sussex Research Online: http://sro.sussex.ac.uk/id/eprint/77355/ This document is made available in accordance with publisher policies and may differ from the published version or from the version of record. If you wish to cite this item you are advised to consult the publisher’s version. Please see the URL above for details on accessing the published version. Copyright and reuse: Sussex Research Online is a digital repository of the research output of the University. Copyright and all moral rights to the version of the paper presented here belong to the individual author(s) and/or other copyright owners. To the extent reasonable and practicable, the material made available in SRO has been checked for eligibility before being made available. Copies of full text items generally can be reproduced, displayed or performed and given to third parties in any format or medium for personal research or study, educational, or not-for-profit purposes without prior permission or charge, provided that the authors, title and full bibliographic details are credited, a hyperlink and/or URL is given for the original metadata page and the content is not changed in any way. http://sro.sussex.ac.uk View Article Online View Journal ChemComm Accepted Manuscript This article can be cited before page numbers have been issued, to do this please use: N. Tsoureas and F. G. Cloke, Chem. Commun., 2018, DOI: 10.1039/C8CC04391D. Volume 52 Number 1 4 January 2016 Pages 1–216 This is an Accepted Manuscript, which has been through the Royal Society of Chemistry peer review process and has been ChemComm accepted for publication. Chemical Communications Accepted Manuscripts are published online shortly after www.rsc.org/chemcomm acceptance, before technical editing, formatting and proof reading. Using this free service, authors can make their results available to the community, in citable form, before we publish the edited article. We will replace this Accepted Manuscript with the edited and formatted Advance Article as soon as it is available. You can find more information about Accepted Manuscripts in the author guidelines. Please note that technical editing may introduce minor changes to the text and/or graphics, which may alter content. The journal’s ISSN 1359-7345 standard Terms & Conditions and the ethical guidelines, outlined in our author and reviewer resource centre, still apply. In no COMMUNICATION Marilyn M. Olmstead, Alan L. Balch, Josep M. Poblet, Luis Echegoyen et al. Reactivity dif erences of Sc3N@C2n (2n = 68 and 80). Synthesis of the fi rst methanofullerene derivatives of Sc N@D -C 3 5h 80 event shall the Royal Society of Chemistry be held responsible for any errors or omissions in this Accepted Manuscript or any consequences arising from the use of any information it contains. rsc.li/chemcomm Page 1 of 5 Please doChemComm not adjust margins View Article Online DOI: 10.1039/C8CC04391D Journal Name COMMUNICATION Activation of Carbon Suboxide (C3O2) by U(III) to form a Cyclobutane-1,3-dione Ring. Received 00th January 20xx, a a Accepted 00th January 20xx Nikolaos Tsoureas and F. Geoffrey N. Cloke DOI: 10.1039/x0xx00000x www.rsc.org/ 5 The activation of C3O2 by the U(III) complex [U(η -Cp’)3] (Cp’ = by our recent success in isolating the first structurally C5H4SiMe3) is described. The reaction results in the reductive authenticated complex of C3O2 en route to its trimerisation 17 coupling of three C3O2 units to form a tetranuclear complex with a mediated by the syn-bimetallic complex (1) (Scheme 1), we central cyclobutane-1,3-dione ring, with concomitant loss of CO. decided to undertake such a study. Careful control of reaction conditions has allowed the trapping of Exposure of olive-green brown toluene solutions of mixed an intermediate, dimeric bridging ketene complex, which sandwich complexes of the general molecular formula [U(η8- 5 Me4R’ i Manuscript undergoes insertion of C3O2 to form the final product. C8H6-{1,4-(SiR3)2})(η -Cp )(THF)x] (R = Me R’ =Me or Pr x =1; i R = Pr, R’ = Me, Et x =1, 0 respectively) to C3O2 (a very detailed The resurgence of non-aqueous uranium chemistry has led to synthesis of C3O2 can be found in ref. 17) at -78 ⁰C in a 1:1 a wide range of novel reactivity towards many important small stoichiometry, resulted in intense brown-red solutions. 1 molecules. Pertinent examples, encompassing both high and However, despite our best efforts, work-up under a range of low valent uranium centres, include the reductive different conditions afforded only intractable solids, that were 2 3 3b homologation of CO, the reductive coupling of CO2, SO2, completely insoluble in common organic solvents. We 4 1,4-(SiR3)2 2- and NO/CO mixtures, conversion of CO to the isocyanate suspected that the [COT ] (COT = C8H6) ligand might 5 6 † anion, the transformation of CO/H2 to the methoxide anion, not be inert to attack by C3O2, in contrast to the Pn supporting 7 † i 17 N2 activation and more recently the electrocatalytic splitting ligand (Pn = C8H4-{1,4-(Si Pr3)2}) (Scheme 1). Therefore, we 8 9 Accepted of H2O as well as the reduction of N2 to NH3. However, the decided to turn our attention to another class of U(III) interaction of carbon suboxide (C3O2) with uranium complexes compounds, namely the tris-cyclopentadienyl complexes. 5 is as yet unexplored. C3O2 is the first in the series of odd The U(III) complex [U(η -Cp’)3] (2) (Cp’ = C5H4SiMe3), first 10 Published on 19 July 2018. Downloaded by University of Sussex 7/19/2018 10:41:53 AM. carbon chain suboxides that are synthetically available. Its synthesised by Andersen et al.,18 was envisaged as a viable physical and spectroscopic properties have been extensively candidate,19 especially in light of the ability of the Cp’ ligand to 10c,11 12 studied both theoretically and experimentally. Although stabilise low valent U(II)20 and Ln(II)21 (Ln = lanthanide) its reactivity with many organic substrates is well complexes. When a green toluene solution of (2) is exposed to 12e, 13 14 established, its coordination chemistry and subsequent C3O2 at -78 ⁰C in a 1:1 ratio an instantaneous color change to 15 metal mediated activation are relatively limited, although the deep-red wine occurs. Work-up under optimised conditions 11a16 latter have recently been examined in silico. Based on the (see ESI), followed by analysis by 1H-NMR spectroscopy of the lack of examples regarding the reactivity of C3O2 with uranium crude reaction mixture, showed the existence of a new major species (3) (ca. ≥ 70%) that displayed two signals in a 1:1 ratio SiiPr Si Si 3 Si Si CO Si OSi O 29 1 Ti corresponding to two SiMe3 resonances. The Si{ H}-NMR ChemComm Ti C Ti O i C3O2 C3O2 C Pr3Si C spectrum also showed only two signals located at -65.60 and - i Ti Ti C Ti Pr3Si Ti Ti O Si Si 69.57 ppm (δ C D ) shifted downfield from -165 ppm for (2), Si O O 6 6 Si Si CSi i C further signifying a change in the oxidation state of the metal Si Pr3 (1) O 22 centre. Scheme 1: Trimerisation of C O mediated by (1) 3 2 Mass spectrometry was uninformative as only fragments complexes (or indeed any other f-elements) and encouraged related to (2) were identifiable. However, crystals suitable for This journal is © The Royal Society of Chemistry 20xx J. Name., 2013, 00, 1-3 | 1 Please do not adjust margins Please doChemComm not adjust margins Page 2 of 5 View Article Online DOI: 10.1039/C8CC04391D COMMUNICATION Journal Name 26 an XRD study were eventually obtained from n-heptane bis(R1R2ylene)cyclobutane-1,3-diones. Finally, the C4-C5 (Figure 1), albeit in low yield. Nevertheless, this crystalline bond length of 1.491(5) Å is in excellent agreement with the material indeed corresponds to the major component of the corresponding C-C bonds found in dispiro[2.1.2.1]octan-4,8- reaction mixture, as confirmed by its 1H and 29Si{1H}-NMR dione,27 dispiro[4.14.1]dodeca-2,9-diene-6,12-dione28 and 1,6- 29 spectra, while its overall symmetry (Ci) is retained in solution diphenyldispiro[2.1.2.1]octane-4,8-dione and the same and accounts for the observed spectra. (3) displays a applies for the C5-O3 bond distance (1.217(5) Å). Based on 5 tetranuclear structure in which four [U(η -Cp’)3] centres are these metrics, a simplified depiction of the bonding in (3) is linked by a complex organic structure containing a central shown in Figure 2. [U] O C C C O [U] O O [U] O C C C O [U] Figure 2. Bonding in (3) ([U]= UCp'3) As can be seen from Figure 2, the formation of (3) can be rationalised by considering two possible pathways shown in Scheme 2. Manuscript CO (i) [U]-OCCCO-[U] O=C=C: C3O2 C3O2 Figure 1: ORTEP diagram of the molecular structure of (3), showing 50% probability ellipsoids. H atoms and methyl groups of the SiMe3 substituents [U] (4) C O have been omitted for clarity.
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