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dc.contributor.advisorArnold, Polly
dc.contributor.advisorLove, Jason
dc.contributor.authorSuvova, Marketa
dc.date.accessioned2018-03-23T12:38:27Z
dc.date.available2018-03-23T12:38:27Z
dc.date.issued2018-07-09
dc.identifier.urihttp://hdl.handle.net/1842/28952
dc.description.abstractThorium(IV) and uranium(IV) coordination complexes have been studied for the last 60 years. They have shown interesting reactivity that is often divergent from that of transition metal complexes, and that also provides an insight into some unanticipated differences between thorium(IV) and uranium(IV). An introduction to thorium(IV) and uranium(IV) organometallic chemistry supported by carbocyclic and N-donor ligands is given in Chapter One. The reactivity of actinide alkyl, amide and alkynyl complexes towards small molecules is discussed and select examples provided. The redox chemistry of thorium and uranium is also introduced. Chapter Two describes the alkylation and amination chemistry of uranium(IV) and thorium(IV) trans-calix[2]benzene[2]pyrrolide ((L)2-) complexes, [(L)AnCl2], yielding new actinide(IV) complexes of the type [M(L-2H)An(R)] (M = Li or K, R = Me, CH2SiMe3, CH2Ph, N(SiMe3)2), where (L)2- undergoes further deprotonation to (L-2H)4-. Additionally, the lability of the [M(L-2H)An(R)] “ate”-complexes towards M+ ion exchange is addressed. Further, the selective ligand reprotonation of (L-2H)4- to (L)2- using HSiR'3 (R' = Me, iPr) and [Et3NH][BPh4] yielding [(L)An(C≡CSiR'3)2] and [(L)An(R)][BPh4] respectively, is explained. The reactivity of these complexes towards amines, silanes, alkenes, tin hydrides, silicone grease, tBuNC, H2, CO, CO2 or CS2 is described. Crystallographic characterisation shows that [(L)Th(N(SiMe3)2)][BPh4] contains an unusual example of a thorium(IV) bis-arene coordination mode. The reactivity of [(L)Th(C≡CSiMe3)2] towards a number of substrates including alkenes, [Ni(COD)2], [Pt(norbornene)3], P4, CO2 or H2 is also discussed. Activation of CO2 by [(L)Th(C≡CSiMe3)2] at 80 °C results in (L)2- functionalisation and abstraction to yield a new tricyclic organic molecule with the general formula LCO. The addition of [Ni(COD)2] to [(L)Th(C≡CSiMe3)2] and PR''3 (R'' = phenyl, cyclohexyl) yields heterobimetallic complexes [(L)Th(C≡CSiMe3)2·Ni(PR''3)]; these products display both dipyrrolic and bis-arene coordination. The changes in ligand coordination mode are discussed alongside DFT computational analyses that have been carried out by collaborators. The substitution reactions of [(L)AnCl2] with NaBH4 to form actinide(IV) borohydride complexes [(L)An(BH4)2] and subsequent attempted abstractions of BH3 from [(L)Th(BH4)2] are presented. Conclusions are provided at the end of the chapter. Chapter Three focusses on the oxidation chemistry of uranium(IV) within the (L)2- and (L-2H)4- ligand framework, prompted by the isolation of a uranium(V) complex [Li[(L)UO2]·LiI] from the oxidation of the uranium(IV) complex [Li(L-2H)U(Me)]. Conclusions are provided at the end of the chapter. Experimental methods and characterising data are given in Chapter Four.en
dc.contributor.sponsorotheren
dc.language.isoenen
dc.publisherThe University of Edinburghen
dc.relation.hasversionM. Suvova, K. T. P. O’Brien, J. H. Farnaby, N. Kaltsoyannis, P. L. Arnold, ‘Thorium(IV) and uranium(IV) trans-calix[2]benzene[2]pyrrolide alkyl and alkynyl complexes: synthesis, reactivity and electronic structure’; Organometallics (Special Issue: Organometallic Actinide and Lanthanide Chemistry ).en
dc.relation.hasversionP. L. Arnold, B. E. Cowie, M. Suvova, M. Zegke, N. Magnani, E. Colineau, J.-C. Griveau, R. Caciuffo, J. B. Love, ‘Axially symmetric U-O-Ln and U-O-U containing molecules from the control of uranyl reduction with simple f-block halides’, Angew. Chem. Int. Ed., 2017, 56, 10775-10779.en
dc.relation.hasversionJ. A. L. Wells, M. L. Seymour, M. Suvova, P. L. Arnold, ‘Dinuclear uranium complexation and manipulation using robust tetraaryloxides’, Dalton Trans., 2016, 45, 16026- 16032. (Themed Issue: Reactions Facilitated by Ligand Design)en
dc.subjecturanium complexesen
dc.subjectthorium complexesen
dc.subjectligand frameworksen
dc.subjectactinide complexesen
dc.subjectcaesium cationen
dc.subjecturanium-oxo complexesen
dc.subjectnuclear wasteen
dc.titleActinide Hydrocarbyl chemistry supported by a small flexible pyrrolic macrocycleen
dc.typeThesis or Dissertationen
dc.type.qualificationlevelDoctoralen
dc.type.qualificationnamePhD Doctor of Philosophyen


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