Themed collection Frontiers of Organo-f-Element Chemistry

26 items
Open Access Editorial

Frontiers of organo-f-element chemistry

A collection of papers presented at the Pacifichem 2015 symposium "Frontiers of Organo-f-Element Chemistry" held in Honolulu, Hawaii, USA.

Graphical abstract: Frontiers of organo-f-element chemistry
From the themed collection: Frontiers of Organo-f-Element Chemistry
Editorial

The structure determination of uranocene and the first COT lanthanide complexes

Uranocene (bis(cyclooctatetraenyl)uranium) began a new chapter of organoactinide and -lanthanide research. This narrative links this chemistry to the current active topics. Adapted with permission from Organometallics, 2004, 23(15), cover. Copyright (2004) American Chemical Society.

Graphical abstract: The structure determination of uranocene and the first COT lanthanide complexes
From the themed collection: Frontiers of Organo-f-Element Chemistry
Perspective

Rare earth–metal bonding in molecular compounds: recent advances, challenges, and perspectives

In this review, all structurally authenticated molecular compounds with direct bonds between rare earth metals and transition or main group metals are summarized. Novel aspects of their syntheses, properties and reactivities are highlighted.

Graphical abstract: Rare earth–metal bonding in molecular compounds: recent advances, challenges, and perspectives
From the themed collection: Frontiers of Organo-f-Element Chemistry
Letter

New air-stable uranium(IV) complexes with enhanced volatility

New volatile uranium(IV) complexes using a heteroarylalkenolate with an elongated fluoroalkyl chain and a tetradentate enaminone as ligands are reported.

Graphical abstract: New air-stable uranium(iv) complexes with enhanced volatility
From the themed collection: Frontiers of Organo-f-Element Chemistry
Letter

Reaction of a bulky amine borane with lanthanide trialkyls. Formation of alkyl lanthanide imide complexes

Lanthanide imidoborane complexes with terminal alkyl groups are synthesized from the reactions of simple lanthanide trialkyls with a bulky amine borane.

Graphical abstract: Reaction of a bulky amine borane with lanthanide trialkyls. Formation of alkyl lanthanide imide complexes
From the themed collection: Frontiers of Organo-f-Element Chemistry
Letter

Reactivity of [U(CH2SiMe2NSiMe3)(NR2)2] (R = SiMe3) with elemental chalcogens: towards a better understanding of chalcogen atom transfer in the actinides

Addition of elemental chalcogens to [U(CH2SiMe2NSiMe3)(NR2)2] results in formation of [U(ECH2SiMe2NSiMe3)(NR2)2] (R = SiMe3; E = S, Se, Te) via chalcogen insertion into the U–C bond.

Graphical abstract: Reactivity of [U(CH2SiMe2NSiMe3)(NR2)2] (R = SiMe3) with elemental chalcogens: towards a better understanding of chalcogen atom transfer in the actinides
From the themed collection: Frontiers of Organo-f-Element Chemistry
Letter

Comments on reactions of oxide derivatives of uranium with hexachloropropene to give UCl4

The reactions of U3O8, UO2(NO3)2·6H2O, and UO2Cl2 with hexachloropropene to make UCl4 are described.

Graphical abstract: Comments on reactions of oxide derivatives of uranium with hexachloropropene to give UCl4
From the themed collection: Frontiers of Organo-f-Element Chemistry
Paper

Computational thermodynamic study on the complexes of Am(III) with tridentate N-donor ligands

BTP differs from hemi-BTP and TPY in its conformational preference, which may contribute to its higher efficiency in extracting Am(III).

Graphical abstract: Computational thermodynamic study on the complexes of Am(iii) with tridentate N-donor ligands
From the themed collection: Frontiers of Organo-f-Element Chemistry
Paper

In situ synthesis of lanthanide complexes supported by a ferrocene diamide ligand: extension to redox-active lanthanide ions

The scope of an in situ method to prepare rare-earth alkyl and halide precursors was extended to cerium, praseodymium, samarium, terbium, thulium, and ytterbium.

Graphical abstract: In situ synthesis of lanthanide complexes supported by a ferrocene diamide ligand: extension to redox-active lanthanide ions
From the themed collection: Frontiers of Organo-f-Element Chemistry
Paper

Grafting of lanthanide complexes on silica surfaces dehydroxylated at 200 °C: a theoretical investigation

The grafting reaction of lanthanide silylamide complexes has been studied, in the framework of the DFT, highlighting the different grafting modes on a silica surface dehydroxylated at 200 °C.

Graphical abstract: Grafting of lanthanide complexes on silica surfaces dehydroxylated at 200 °C: a theoretical investigation
From the themed collection: Frontiers of Organo-f-Element Chemistry
Open Access Paper

Rare earth 3-(4′-hydroxyphenyl)propionate complexes

Structural variation of lanthanoid 3-(4′-hydroxyphenyl)propionates and investigation of the anti-corrosion properties of lanthanum 3-(4′-hydroxyphenyl)propionate are presented, highlighting lanthanoid contraction and the importance of the –CH[double bond, length as m-dash]CH− structural unit of 4-hydroxycinnamates in corrosion mitigation.

Graphical abstract: Rare earth 3-(4′-hydroxyphenyl)propionate complexes
From the themed collection: Frontiers of Organo-f-Element Chemistry
Paper

Rare-earth metal alkyl complexes bearing an alkoxy N-heterocyclic carbene ligand: synthesis, characterization, catalysis for isoprene polymerization

The new rare-earth metal alkyl complexes bearing alkoxy NHC ligands were prepared, which showed moderate cis-1,4 selectivity for isoprene polymerization.

Graphical abstract: Rare-earth metal alkyl complexes bearing an alkoxy N-heterocyclic carbene ligand: synthesis, characterization, catalysis for isoprene polymerization
From the themed collection: Frontiers of Organo-f-Element Chemistry
Paper

Synthesis and structural characterization of amido heteroscorpionate rare-earth metal complexes and hydroamination of aminoalkenes

New amide heteroscorpionate rare-earth complexes were developed and used as efficient catalysts for the intramolecular hydroamination of aminoalkenes.

Graphical abstract: Synthesis and structural characterization of amido heteroscorpionate rare-earth metal complexes and hydroamination of aminoalkenes
From the themed collection: Frontiers of Organo-f-Element Chemistry
Paper

Synthesis and characterization of bis(amidate) rare-earth metal amides and their application in catalytic addition of amines to carbodiimides

Five bis(amidate) rare-earth metal amides were successfully employed in guanidination, and the Nd-based catalyst showed the highest reactivity.

Graphical abstract: Synthesis and characterization of bis(amidate) rare-earth metal amides and their application in catalytic addition of amines to carbodiimides
From the themed collection: Frontiers of Organo-f-Element Chemistry
Open Access Paper

One ligand fits all: lanthanide and actinide sandwich complexes comprising the 1,4-bis(trimethylsilyl)cyclooctatetraenyl (=COT′′) ligand

Twelve new lanthanide and actinide sandwich complexes containing the 1,4-bis(trimethylsilyl)cyclooctatetraenyl ligand (COT′′) have been prepared and structurally characterized by X-ray diffraction.

Graphical abstract: One ligand fits all: lanthanide and actinide sandwich complexes comprising the 1,4-bis(trimethylsilyl)cyclooctatetraenyl (=COT′′) ligand
From the themed collection: Frontiers of Organo-f-Element Chemistry
Paper

Half-sandwich rare-earth metal tris(alkyl) ate complexes catalyzed phosphaguanylation reaction of phosphines with carbodiimides: an efficient synthesis of phosphaguanidines

Half-sandwich Y/Li ate complex displays better catalytic activity for phosphaguanylation reaction of phosphines with carbodiimides than the neutral yttrium complexes.

Graphical abstract: Half-sandwich rare-earth metal tris(alkyl) ate complexes catalyzed phosphaguanylation reaction of phosphines with carbodiimides: an efficient synthesis of phosphaguanidines
From the themed collection: Frontiers of Organo-f-Element Chemistry
Open Access Paper

Reactivity of halfsandwich rare-earth metal methylaluminates toward potassium (2,4,6-tri-tert-butylphenyl)amide and 1-adamantylamine

Donor functionalities drastically affect salt-metathetical methylaluminato–amido exchange reactions in CpRLn(AlMe4)2 by triggering methylaluminate cleavage and C–H bond activation of proximal aliphatic groups.

Graphical abstract: Reactivity of halfsandwich rare-earth metal methylaluminates toward potassium (2,4,6-tri-tert-butylphenyl)amide and 1-adamantylamine
From the themed collection: Frontiers of Organo-f-Element Chemistry
Open Access Paper

A structural investigation of heteroleptic lanthanide substituted cyclopentadienyl complexes

The synthesis and structural authentication of novel heteroleptic lanthanide complexes supported by bulky cyclopentadienyl ligands is herein presented. Steric effects play a fundamental role in the coordination motifs.

Graphical abstract: A structural investigation of heteroleptic lanthanide substituted cyclopentadienyl complexes
From the themed collection: Celebrating our 2018 prize and award winners
Paper

Heterometallic rare-earth metal complexes with imino-functionalized 8-hydroxyquinolyl ligands: synthesis, characterization and catalytic activity towards hydrophosphinylation of trans-β-nitroalkene

The heterobimetallic complexes exhibited high catalytic activities on the hydrophosphinylation of β-nitroalkenes.

Graphical abstract: Heterometallic rare-earth metal complexes with imino-functionalized 8-hydroxyquinolyl ligands: synthesis, characterization and catalytic activity towards hydrophosphinylation of trans-β-nitroalkene
From the themed collection: Frontiers of Organo-f-Element Chemistry
Open Access Paper

Investigation of the “bent sandwich-like” divalent lanthanide hydro-tris(pyrazolyl)borates Ln(TpiPr2)2 (Ln = Sm, Eu, Tm, Yb)

Synthesis, luminescence and reactivity of the lanthanide(II) “bent sandwich-like” hydro-tris(pyrazolyl)borate complexes Ln(TpiPr2)2 (Ln = Sm, Eu, Tm, Yb) have been investigated.

Graphical abstract: Investigation of the “bent sandwich-like” divalent lanthanide hydro-tris(pyrazolyl)borates Ln(TpiPr2)2 (Ln = Sm, Eu, Tm, Yb)
From the themed collection: Frontiers of Organo-f-Element Chemistry
Paper

Rare-earth–iridium heterobimetallic complexes with bridging imido and silylmethyl ligands: synthesis, structure and reactivity

The reaction of [(C5Me5)Ir[double bond, length as m-dash]NtBu] with [(C5Me4R)Ln(CH2SiMe3)2(THF)] (Ln = Lu, Sc; R = Me, SiMe3) afforded novel heterometallic rare earth–iridium imido complexes, which show unique structural features and reactivities.

Graphical abstract: Rare-earth–iridium heterobimetallic complexes with bridging imido and silylmethyl ligands: synthesis, structure and reactivity
From the themed collection: Frontiers of Organo-f-Element Chemistry
Open Access Paper

Activation of carbon dioxide by new mixed sandwich uranium(III) complexes incorporating cyclooctatetraenyl and pyrrolide, phospholide, or arsolide ligands

Mixed-sandwich complexes of the type [U(COTTIPS2)(CpEMe4)] (where E is N or P and COTTIPS2 = C8H6{1,4-SiiPr3}) both reduce and insert CO2 to afford dimeric, oxo-bridged, uranium carbamate and phosphacarbonate complexes.

Graphical abstract: Activation of carbon dioxide by new mixed sandwich uranium(iii) complexes incorporating cyclooctatetraenyl and pyrrolide, phospholide, or arsolide ligands
From the themed collection: Frontiers of Organo-f-Element Chemistry
Paper

Dithionite and sulfinate complexes from the reaction of SO2 with decamethylsamarocene

The reaction of [(η5-C5Me5)2Sm(THF)2] with SO2 resulted in dithionite, sulfinate and mixed dithionite–sulfinate complexes.

Graphical abstract: Dithionite and sulfinate complexes from the reaction of SO2 with decamethylsamarocene
From the themed collection: Frontiers of Organo-f-Element Chemistry
Open Access Paper

Synthesis and catalytic activity of homoleptic lanthanide-tris(cyclopropylethinyl)amidinates

New unsolvated, homoleptic lanthanide(III) tris(cyclopropylethinylamidinate) complexes of the type [c-C3H5–C[triple bond, length as m-dash]C–C(NR)2]3Ln (R = iPr, cyclohexyl; Ln = Nd, Sm, Ho) have been prepared and the crystal structure of the holmium derivative [c-C3H5–C[triple bond, length as m-dash]C–C(NiPr)2]3Ho has been confirmed by X-ray diffraction.

Graphical abstract: Synthesis and catalytic activity of homoleptic lanthanide-tris(cyclopropylethinyl)amidinates
From the themed collection: Frontiers of Organo-f-Element Chemistry
Paper

Rare-earth metal bis(alkyl) complexes bearing pyrrolidinyl-functionalized cyclopentadienyl, indenyl and fluorenyl ligands: synthesis, characterization and the ligand effect on isoprene polymerization

The ligand effect on isoprene polymerization was investigated using rare-earth metal bis(alkyl) complexes bearing pyrrolidinyl-functionalized cyclopentadienyl, indenyl and fluorenyl ligands.

Graphical abstract: Rare-earth metal bis(alkyl) complexes bearing pyrrolidinyl-functionalized cyclopentadienyl, indenyl and fluorenyl ligands: synthesis, characterization and the ligand effect on isoprene polymerization
From the themed collection: Frontiers of Organo-f-Element Chemistry
Paper

Substitution reaction of triphenylphosphine oxide with rare-earth metal phosphido methyl complexes

Rare-earth metal phosphido methyl complexes [LLn(Me){P(H)Ar}] react with triphenylphosphine oxide to give [LLn(Ph){CH2P(O)Ph2}], indicating C(alkyl)–P bond formation and C(aryl)–P bond cleavage.

Graphical abstract: Substitution reaction of triphenylphosphine oxide with rare-earth metal phosphido methyl complexes
From the themed collection: Frontiers of Organo-f-Element Chemistry
26 items

About this collection

This themed collection on organo-f-element chemistry was guest edited by Frank Edelmann and Peter Junk. It begins with a historical note on the first COT lanthanide complexes by Kenneth Raymond, includes a Perspective review by Mikhail Butovskiy and Rhett Kempe on rare earth–metal bonding in molecular compounds, and is completed by 23 original research papers that provide an overview of recent developments at the 'frontiers' of organo-f-element chemistry.

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