title: Mixed sandwich thorium complexes incorporating bis(tri-isopropylsilyl)cyclooctatetraenyl and pentamethylcyclopentadienyl ligands: synthesis, structure and reactivity.
abstract: The Th(iv) mixed-sandwich halide complexes Th(COT(TIPS2))Cp*X (where COT(TIPS2) = 1,4-{Si(i)Pr(3)}(2)C(8)H(6), X = Cl, I) have been synthesised, and structurally characterised. When Th(COT(TIPS2))Cp*I is reduced in situ in the presence of CO(2), a mixture of dimeric carboxylate and oxalate complexes {Th(COT(TIPS2))Cp*}(2)(μ-κ(1):κ(2)-CO(3)) and {Th(COT(TIPS2))Cp*}(2)(μ-κ(2):κ(2)-C(2)O(4)) are formed, possibly via a transient Th(iii) species. Th(COT(TIPS2))Cp*Cl is readily alkylated to yield the benzyl complex Th(COT(TIPS2))Cp*CH(2)Ph, which reacts with CO(2) to form a carboxylate and with H(2) to form a hydride; the latter inserts CO(2), giving the bridging formate complex {Th(COT(TIPS2))Cp*(μ-κ(1):κ(1)-O(2)CH)}(2).
authors.affiliation: Department of Chemistry, School of Life Sciences, University of Sussex, Brighton, BN1 9QJ, UK. f.g.cloke@sussex.ac.uk.
authors.forename: Zoë E
authors.initials: ZE
authors.lastname: Button
authors.forename: Jessica A
authors.initials: JA
authors.lastname: Higgins
authors.forename: Markéta
authors.initials: M
authors.lastname: Suvova
authors.forename: F Geoffrey N
authors.initials: FG
authors.lastname: Cloke
authors.forename: S Mark
authors.initials: SM
authors.lastname: Roe
mesh_terms: D003517:Cyclopentanes / Q000737:chemistry*; D008024:Ligands; D008958:Models, Molecular; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry*; D017646:Organosilicon Compounds / Q000737:chemistry*; D013910:Thorium / Q000737:chemistry*
chemical_list: D003517:Cyclopentanes; D008024:Ligands; D009942:Organometallic Compounds; D017646:Organosilicon Compounds; D013910:Thorium