Themed collection Frontiers of Organo-f-Element Chemistry
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.
New J. Chem., 2015,39, 7539-7539
https://doi.org/10.1039/C5NJ90042E
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.
New J. Chem., 2015,39, 7540-7543
https://doi.org/10.1039/C5NJ00533G
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.
New J. Chem., 2015,39, 7544-7558
https://doi.org/10.1039/C5NJ00802F
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.
New J. Chem., 2015,39, 7571-7574
https://doi.org/10.1039/C5NJ00647C
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.
New J. Chem., 2015,39, 7567-7570
https://doi.org/10.1039/C5NJ01067E
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.
New J. Chem., 2015,39, 7563-7566
https://doi.org/10.1039/C5NJ00739A
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.
New J. Chem., 2015,39, 7559-7562
https://doi.org/10.1039/C5NJ00476D
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).
New J. Chem., 2015,39, 7716-7729
https://doi.org/10.1039/C5NJ01285F
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.
New J. Chem., 2015,39, 7696-7702
https://doi.org/10.1039/C5NJ01402F
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.
New J. Chem., 2015,39, 7703-7715
https://doi.org/10.1039/C5NJ01645B
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 –CHCH− structural unit of 4-hydroxycinnamates in corrosion mitigation.
New J. Chem., 2015,39, 7688-7695
https://doi.org/10.1039/C5NJ00787A
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.
New J. Chem., 2015,39, 7682-7687
https://doi.org/10.1039/C5NJ00737B
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.
New J. Chem., 2015,39, 7672-7681
https://doi.org/10.1039/C5NJ00930H
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.
New J. Chem., 2015,39, 7667-7671
https://doi.org/10.1039/C5NJ00506J
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.
New J. Chem., 2015,39, 7656-7666
https://doi.org/10.1039/C5NJ00991J
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.
New J. Chem., 2015,39, 7649-7655
https://doi.org/10.1039/C5NJ01136A
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.
New J. Chem., 2015,39, 7640-7648
https://doi.org/10.1039/C5NJ00800J
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.
New J. Chem., 2015,39, 7633-7639
https://doi.org/10.1039/C5NJ00761E
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.
New J. Chem., 2015,39, 7626-7632
https://doi.org/10.1039/C5NJ00409H
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.
New J. Chem., 2015,39, 7617-7625
https://doi.org/10.1039/C5NJ00568J
Rare-earth–iridium heterobimetallic complexes with bridging imido and silylmethyl ligands: synthesis, structure and reactivity
The reaction of [(C5Me5)IrNtBu] 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.
New J. Chem., 2015,39, 7608-7616
https://doi.org/10.1039/C5NJ00598A
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.
New J. Chem., 2015,39, 7602-7607
https://doi.org/10.1039/C5NJ00590F
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.
New J. Chem., 2015,39, 7589-7594
https://doi.org/10.1039/C5NJ00318K
Synthesis and catalytic activity of homoleptic lanthanide-tris(cyclopropylethinyl)amidinates
New unsolvated, homoleptic lanthanide(III) tris(cyclopropylethinylamidinate) complexes of the type [c-C3H5–CC–C(NR)2]3Ln (R = iPr, cyclohexyl; Ln = Nd, Sm, Ho) have been prepared and the crystal structure of the holmium derivative [c-C3H5–CC–C(NiPr)2]3Ho has been confirmed by X-ray diffraction.
New J. Chem., 2015,39, 7595-7601
https://doi.org/10.1039/C5NJ00555H
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.
New J. Chem., 2015,39, 7575-7581
https://doi.org/10.1039/C5NJ00279F
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.
New J. Chem., 2015,39, 7582-7588
https://doi.org/10.1039/C5NJ00335K
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.