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분자활성 촉매반응 연구단
분자활성 촉매반응 연구단
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C-H Bond Addition across a Transient Uranium-Nitrido Moiety and Formation of a Parent Uranium Imido Complex

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Title
C-H Bond Addition across a Transient Uranium-Nitrido Moiety and Formation of a Parent Uranium Imido Complex
Author(s)
Mullane, KC; Ho Ryu; Cheisson, T; Grant, LN; Ji Young Park; Manor, BC; Carroll, PJ; Mu-Hyun Baik; Mindiola, DJ; Schelter, EJ
Publication Date
2018-09
Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, v.140, no.36, pp.11335 - 11340
Publisher
AMER CHEMICAL SOC
Abstract
Uranium complexes in the +3 and +4 oxidation states were prepared using the anionic PN- (PN- = (N-(2-(diisopropylphosphino) -4-methylphenyl)-2,4,6-trimethylanilide) ligand framework. New complexes include the halide starting materials, (PN)(2)(UI)-I-III (1) and (PN)(2)(UCl2)-Cl-IV (2), which both yield (PN)(2)U-IV(N-3)(2) (3) by reaction with NaN3. Compound 3 was reduced with potassium graphite to produce a putative, transient uranium-nitrido moiety that underwent an intramolecular C-H activation to form a rare example of a parent imido complex, [K(THF)(3)][(PN)U-IV(= NH)[(Pr2P)-Pr-i(C6H3Me)N(C6H2Me2CH2)]] (4). Calculated reaction energy profiles strongly suggest that a C-H insertion becomes unfavorable when a reductant is present, offering a distinctively different reaction pathway than previously observed for other uranium nitride complexes. © 2018 American Chemical Society
URI
https://pr.ibs.re.kr/handle/8788114/5918
ISSN
0002-7863
Appears in Collections:
Center for Catalytic Hydrocarbon Functionalizations(분자활성 촉매반응 연구단) > Journal Papers (저널논문)
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