Oxidation in Nonclassical Organolanthanide Chemistry:  Synthesis, Characterization, and X-ray Crystal Structures of Cerium(III) and -(IV) Amides

Hitchcock, Peter B.; Hulkes, and Alexander G.; Läppert, Michael F.

doi:10.1021/ic035100v

Cited by 65 publications

(54 citation statements)

References 45 publications

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“…[20] Fewer than 30 species met this criteria,[55, 56, 77–87] with the majority being monomers solvated by either THF[78, 81, 88] or DME[78, 80, 81]. Additionally, we have isolated a number of solvated LnX 3 species that add to this family, including: [ScBr 3 (THF) 3 ] ( S1 ), [NdBr 3 (solv) 4 ] solv = THF ( S2 ) and py ( S3 ).…”

Section: Resultsmentioning

confidence: 99%

Structural characterization of methanol substituted lanthanum halides

Boyle¹,

Ottley²,

Alam³

et al. 2010

Polyhedron

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The first study into the alcohol solvation of lanthanum halide [LaX 3 ] derivatives as a means to lower the processing temperature for the production of the LaBr 3 scintillators was undertaken using methanol (MeOH) Publisher's Disclaimer: This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final citable form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain. NIH Public Access Author ManuscriptPolyhedron. Author manuscript; available in PMC 2011 May 10. NIH-PA Author ManuscriptNIH-PA Author Manuscript NIH-PA Author Manuscript indicated that the bulk material for 5 appear to have multiple solvated species, 6 is consistent with the single crystal, and 7 was too broad to elucidate structural aspects. Multinuclear NMR ( 139 La) indicated that these compounds do not retain their structure in MeOD. TGA/DTA data revealed that the de-solvation temperatures of the MeOH derivatives 4 -6 were slightly higher in comparison to their hydrated counterparts.

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Section: Resultsmentioning

confidence: 99%

Structural characterization of methanol substituted lanthanum halides

Boyle¹,

Ottley²,

Alam³

et al. 2010

Polyhedron

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“…Keywords: actinides · computational chemistry · covalency · lanthanides · N-heterocyclic carbenes (24-30 %) yield by oxidation of the common silylamido reagent [CeA C H T U N G T R E N N U N G (N'') 3 ] with TeX 4 (X = Cl or Br) or PBr 2 Ph 3 , molecular halogens resulting in no reaction. [19] Examples of organometallic Ce IV complexes are also rare. The synthesis of [CeA C H T U N G T R E N N U N G (cot) 2 ] [28] (cot = cyclooctatetraenyl) and related complexes, [29][30][31] combining a highly oxidising metal cation with a reducing anionic ligand, has led to intensive study and debate into assignment of the metal oxidation state.…”

Section: ] (Nn' = [N-mentioning

confidence: 99%

Covalency in Ce^IV and U^IV Halide and N‐Heterocyclic Carbene Bonds

Arnold

Turner

Kaltsoyannis

et al. 2010

Chemistry A European J

138

121

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Oxidative halogenation with trityl chloride provides convenient access to Ce(IV) and U(IV) chloroamides [M(N{SiMe(3)}(2))(3)Cl] and their N-heterocyclic carbene derivatives, [M(L)(N{SiMe(3)}(2))(2)Cl] (L = OCMe(2)CH(2)(CNCH(2)CH(2)NDipp) Dipp = 2,6-iPr(2)C(6)H(3)). Computational analysis of the bonding in these and a fluoro analogue, [U(L)(N{SiMe(3)}(2))(2)F], provides new information on the covalency in this relative rare oxidation state for molecular cerium complexes. Computational studies reveal increased Mayer bond orders in the actinide carbene bond compared with the lanthanide carbene bond, and natural and atoms-in-molecules analyses suggest greater overall ionicity in the cerium complexes than in the uranium analogues.

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“…The isolation of Ce[N(SiMe 3 ) 2 ] 3 Cl in moderate yields from the reaction of Ce[N(SiMe 3 ) 2 ] 3 and the rather unusual oxidant TeCl 4 by Lappert and co‐workers marked another breakthrough . Later, the halide complexes Ce[N(SiMe 3 ) 2 ] 3 X (X=F, Br, I) were synthesized by using either Ph 3 CBF 4 and Ph 3 PBr 2 as oxidants or SiMe 3 I in a halogenido exchange reaction. Recently, the high fluorophilicity of silyl groups was exploited by Schelter and co‐workers in the reaction of Ce[N(SiMe 3 ) 2 ] 3 F with Me 3 SiX, and further used for the synthesis of pseudo‐halogenide Ce[N(SiMe 3 ) 2 ] 3 N 3 .…”

Section: Introductionmentioning

confidence: 99%

Ceric Cyclopentadienides Bearing Alkoxy, Aryloxy, Chlorido, or Iodido Co‐Ligands

Schneider

Harmgarth

Edelmann

et al. 2017

Chemistry A European J

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A series of heteroleptic tris(cyclopentadienyl) CeIV complexes has been isolated and crystallographically characterized, revealing the broad accessibility of such organocerium(IV) compounds. The oxidation of complexes CpMe3Ce(thf) and Cp′3Ce(thf) (CpMe=C5H4Me, Cp′=C5H4SiMe3), bearing monosubstituted electron‐poor cyclopentadienyl ligands, with 0.5 equivalents of 1,4‐benzoquinone or C2Cl6 gave the cerium(IV) hydroquinolate complexes CpMe3Ce(OC6H4O)CeCpMe3 and Cp′3Ce(OC6H4O)CeCp′3, or the chloride complexes CpMe3CeCl and Cp′3CeCl, respectively; the iodide complex Cp′3CeI was obtained from the reaction of Cp′3Ce(thf) with elemental iodine. The behavior of Cp′3CeCl in salt metathesis protocols employing alkali metal amides or alkyl, alkoxide, and aryloxide reagents was investigated, which gave rise to the robust and isolable cerium(IV) alkoxide Cp′3Ce(OtBu). Trivalent [Cp′2CeCl]2 was synthesized by AlMe4→Cl exchange utilizing Cp′2Ce(AlMe4) and AlMe2Cl. The reactivity of [Cp′2CeCl]2 towards the oxidants Ph3CCl, C2Cl6, 1,4‐benzoquinone, and I2 has been assessed, and has provided useful information on CeIII/CeIV redox deactivation pathways. In addition to X‐ray structure analysis, all the complexes were characterized by NMR, DRIFT (diffuse reflectance IR Fourier transform), and UV/Vis spectroscopy as well as elemental analysis. The tetravalent compounds were further analyzed for their magnetic susceptibility by using Evans’ method.

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Oxidation in Nonclassical Organolanthanide Chemistry: Synthesis, Characterization, and X-ray Crystal Structures of Cerium(III) and -(IV) Amides

Cited by 65 publications

References 45 publications

Structural characterization of methanol substituted lanthanum halides

Structural characterization of methanol substituted lanthanum halides

Covalency in Ce^IV and U^IV Halide and N‐Heterocyclic Carbene Bonds

Ceric Cyclopentadienides Bearing Alkoxy, Aryloxy, Chlorido, or Iodido Co‐Ligands

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Oxidation in Nonclassical Organolanthanide Chemistry: Synthesis, Characterization, and X-ray Crystal Structures of Cerium(III) and -(IV) Amides

Cited by 65 publications

References 45 publications

Structural characterization of methanol substituted lanthanum halides

Structural characterization of methanol substituted lanthanum halides

Covalency in CeIV and UIV Halide and N‐Heterocyclic Carbene Bonds

Ceric Cyclopentadienides Bearing Alkoxy, Aryloxy, Chlorido, or Iodido Co‐Ligands

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Covalency in Ce^IV and U^IV Halide and N‐Heterocyclic Carbene Bonds