Actinide Organometallic Chemistry

Marks, Tobin J.

doi:10.1126/science.217.4564.989

Cited by 111 publications

(33 citation statements)

References 87 publications

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“…When (bis)pentamethylcyclopentadienylthorium and uranium dichlorides are reacted with appropriate Grignard reagents, Compounds [(CH3)5C5]2ThR2 and [(CH3)sCs]2UR2 can be synthesized( Fig. 1, right) [15,16]. The Th-R and U-R bonds (R = alkyl or amide) are strong a bonds, relatively strong because only two bulky 7r-bonded(CH3)5Cs ligands can be accommodated in the Th^"^ or U^"^ coordination sphere along with two small a-bonded R ligands.…”

Section: Protactiniummentioning

confidence: 99%

Advances in Chemistry of the Actinide Elements

Morss

1984

Radiochimica Acta

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Recent research accomplishments that elucidate the bonding and reactivity of the actinides are highlighted in this review. Improved syntheses of protactinium and transplutonium metals and Compounds have led to determination of physical properties that reveal effects of 5f interactions. Theimodynamic measurements on metals, aqueous ions, and oxides have yielded more systematic understanding of the chemistry of the entire actinide series. Advances in bonding include the preparation of new organoactinide Compounds with strong a and TT metal-carbon and metal-hydrogen bonds; the development of new actinide complexing, sequestering, and extracting agents; and the study of chemical consequences of radioactive decay on oxides and halides. New techniques that impact actinide chemistry are laser fluorescence and photochemistry, radiocoulometry, and pulse radiolysis. Progress has also been made in outlining the basic chemical behavior of the heaviest actinides and the transactinides.Two isomorphs of ThBr4 are known, the well-known /3-ThBr4 and a low-temperature, poorly-characterized a-ThBr4. Below 92 K, j3-ThBr4 displays Splitting of a Raman Vibration and of a bromine nuclear quadrupole resonance line, and new X-ray and neutron diffraction lines appear [2,7]. These observations are not consistent with any conventional superlattice of the tetragonal unit cell, and are caused by a second-order phase transition in which bromine atoms along the c ciystallographic axis are displaced sinusoidally from their sites with a repeating distance of 3.201 c. This phenomenon is a subject of intense investigation and illustrates how careful measurements on pure, Single ciystals can reveal new scientific ideas.

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Section: Protactiniummentioning

confidence: 99%

Advances in Chemistry of the Actinide Elements

Morss

1984

Radiochimica Acta

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“…The synthesis of this enediolate likely proceeds through a bis(g 2 -acyl) species, the presence of which was not observed by 1 H NMR studies. In solution, the nuclearity of the enediolate 22 is assumed to be mononuclear; however, there are early transition metal enediolates reported in both monomeric and dimeric forms (Scheme 8), depending on the steric bulk of the alkyl group [23]. For example, when the alkyl group is bulky (R = CH 2 C(CH 3 ) 3 , CH 2 Si(CH 3 ) 3 ) monomeric species have been observed, and with smaller groups (R = H, CH 3 , CH 2 Ph), higher nuclearity species have been reported.…”

Section: Formation Of a Hafnium Vinyl-enolate And Enediolate Metallacmentioning

confidence: 99%

“…It has been shown that the nature of carbonylation products is dependent on substituents on the metal [23]. With this in mind, the carbonylation of the hafnium diisobutyl complex, 11, was investigated.…”

Section: Formation Of a Hafnium Vinyl-enolate And Enediolate Metallacmentioning

confidence: 99%

Synthesis and reactivity of zirconium and hafnium complexes incorporating chelating diamido-N-heterocyclic-carbene ligands

Spencer

Fryzuk

2005

Journal of Organometallic Chemistry

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“…Aufgrund der überwiegend ionischen Wechselwirkungen sind Uran‐Ligand‐Bindungen häufig instabil und können daher sehr verschiedene Reaktionen eingehen 51. Salz‐, Amin‐ und Alkaneliminierungsreaktionen sind häufig.…”

Section: Periodizität Und Physikochemische Eigenschaftenunclassified

Die Renaissance der nichtwässrigen Uranchemie

Liddle

2015

Angewandte Chemie

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Bis zum Jahr 2000 umfasste die nichtwässrige Uranchemie hauptsächlich Metallocen‐ und klassische Alkyl‐, Amid‐ oder Alkoxidverbindungen sowie bekannte Carben‐, Imido‐ und Oxoderivate. Seither hat das Gebiet einen starken Aufschwung erfahren, einhergehend mit der Entwicklung von Hilfsliganden, mehrfach bindenden Ligandenarten, der Aktivierung niedermolekularer Verbindungen und der Untersuchung magnetischer Eigenschaften. Dieser Aufsatz führt in die theoretischen Grundlagen des Gebiets ein, behandelt wichtige Ausgangsstoffe und untersucht neuere Ligandenklassen für Uran, einschließlich Alkyle, Aryle, Arene, Carbene, Amide, Imide, Nitride, Alkoxide, Aryloxide und Oxoeinheiten. Des Weiteren werden die Fortschritte auf dem Gebiet des Einzelmolekülmagnetismus beschrieben, bevor eine Zusammenfassung der Koordination und Aktivierung niedermolekularer Verbindungen, einschließlich Kohlenmonoxid, Kohlendioxid, Stickstoffmonoxid, Distickstoff, weißem Phosphor und Alkanen, gegeben wird.

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Actinide Organometallic Chemistry

Cited by 111 publications

References 87 publications

Advances in Chemistry of the Actinide Elements

Advances in Chemistry of the Actinide Elements

Synthesis and reactivity of zirconium and hafnium complexes incorporating chelating diamido-N-heterocyclic-carbene ligands

Die Renaissance der nichtwässrigen Uranchemie

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