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Actinides: Amido Complexes

2018· other· en· W2905244993 on OpenAlexaff
David J. H. Emslie

Bibliographic record

VenueEncyclopedia of Inorganic and Bioinorganic Chemistry · 2018
Typeother
Languageen
FieldChemistry
TopicRadioactive element chemistry and processing
Canadian institutionsMcMaster University
Fundersnot available
KeywordsChemistryUranylDenticityHomolepticActinideLigand (biochemistry)Reactivity (psychology)Coordination complexMedicinal chemistryLanthanideInorganic chemistryStereochemistryMetalOrganic chemistryIon

Abstract

fetched live from OpenAlex

Abstract This article reviews progress in actinide amido chemistry, highlighting the role of amido anions as constituents of robust supporting ligands and as reactive ligands. The synthesis, structures, and reactivity of homoleptic actinide complexes in oxidation states III–VI are initially reviewed. Reactivity developed using an ancillary ligand set composed of three bulky monodentate amido anions is then discussed, followed by the chemistry of N(CH 2 CH 2 NSiR 3 ) 3 (Tren X ) and HC(SiMe 2 NAr) 3 (Ts X ) ligands, which feature three amido anions within a multidentate ligand framework. These trisamido ligand platforms have been used to develop a remarkable breadth of actinide chemistry, including terminal UE and U(η 2 ‐E 2 ) linkages (E = S, Se, or Te), the first terminal nitrido complexes of uranium(V) and (VI), a unique nitrido analogue of the uranyl anion [NUO] + , the only terminal PH and AsH complexes of a d‐ or f‐element, and the first metal complex containing the elusive As 2 H 2 molecule. Complexes of tridentate pincer ligands are also described, with a focus on organometallic derivatives, as are bidentate ligands, including redox‐active NN and NO donors. Actinide complexes of polypyrrolyl ligands containing up to eight nitrogen donors are then outlined, including a neptunium(II) complex and a highly reducing thorium(II) synthetic equivalent. Furthermore, bimetallic “Pacman”‐style uranyl complexes are reviewed, providing examples of a cis ‐uranyl linkage, as well as reduction and functionalization of the normally inert uranyl dication. Finally, additional facets of amido ligand reactivity are discussed, including alternative pathways to synthesize actinide amido complexes and the role of actinide–amido complexes in catalysis.

Fetched live from OpenAlex and de-inverted. Abstracts are not stored in this database: the inverted indexes are 8.6 GB of the frame’s 9.3 GB of text, and the host has 13 GB free.

How this classification was reachedexpand

Full frame distilled prediction

Teacher imitation

Not calibrated prevalence, not ground truth. Human validation pending. Learned from the 10,348 direct Codex labels and 10,348 direct Gemma labels. Candidate is the union of thresholded teacher heads; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels or direct frontier model labels.

metaresearch head score (Codex)0.000
metaresearch head score (Gemma)0.000
Version: codex-gemma-dda1882f352aValidation status: machine_predicted_unvalidated
Candidate categoriesMeta-epidemiology (narrow), Insufficient payload (model declined to judge)
Consensus categoriesnone
DomainCandidate signal: none · Consensus signal: none
Study designCandidate signal: Bench or experimental · Consensus signal: Bench or experimental
GenreCandidate signal: Other · Consensus signal: Other
Teacher disagreement score0.153
Threshold uncertainty score0.999

Codex and Gemma teacher scores by category

CategoryCodexGemma
Metaresearch0.0000.000
Meta-epidemiology (narrow)0.0010.001
Meta-epidemiology (broad)0.0010.000
Bibliometrics0.0000.000
Science and technology studies0.0000.001
Scholarly communication0.0000.000
Open science0.0010.000
Research integrity0.0010.001
Insufficient payload (model declined to judge)0.1250.000

Machine scores (provisional)

The two teacher heads of the student model, read on this work. A score orders the frame for review; it never asserts a category, and the validation status ships verbatim with every row.

Baseline scores from an immature model (maturity gate not passed, 7 training rounds). Scores rank; they never assert a category.

Opus teacher head0.007
GPT teacher head0.226
Teacher spread0.219 · how far apart the two teachers sit on this one work
Validation statusscore_only:v0-immature-baseline · verbatim from the scoring run: score_only means the number may rank works, and no category label ships from it

Classification

machine, unvalidated

Machine predicted; a candidate call from one teacher head, not a consensus.

Study designBench or experimental
Domainnot available
GenreOther

How this classification was reached, model by model and score by score, is at the end of the page under "How this classification was reached".

Quick stats

Citations0
Published2018
Admission routes1
Has abstractyes

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