Mixed‐Donor Amido–Siloxo Actinide(IV) Halide and Alkyl Complexes with an Aryl C<i><sub>ipso</sub></i> Interaction

Hayes, Cassandra; Gill, Dayle E.; Brown, Matthew L.; Leznoff, Daniel B.

doi:10.1002/ejic.201402226

Cited by 3 publications

(1 citation statement)

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“…of either LiCH 2 SiMe 3 or NaCp to the uranium "ate" complex results in amido-siloxo uranium diorgano complexes as shown in Scheme 134, which demonstrates that these mixed-donor actinide "ate" complexes can be alkylated to give salt-free diorgano products. [140] Using the same pyridine(diimine) ligand system, a series of reduced pyridine(diimine) uranium(IV) species with either the Cp * or Cp P framework have been generated from uranium(III) starting materials (Scheme 145). The entries in the series differed in the extent of pyridine(diimine) ligand reduction, which was made possible by treatment with potassium graphite.…”

Section: Other Organolanthanide-catalyzed Reactionsmentioning

confidence: 99%

Lanthanides and actinides: Annual survey of their organometallic chemistry covering the year 2014

Edelmann

2016

Coordination Chemistry Reviews

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Section: Other Organolanthanide-catalyzed Reactionsmentioning

confidence: 99%

Lanthanides and actinides: Annual survey of their organometallic chemistry covering the year 2014

Edelmann

2016

Coordination Chemistry Reviews

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Actinides: Amido Complexes

Emslie

2018

Encyclopedia of Inorganic and Bioinorganic Chemistry

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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.

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Main group metal coordination chemistry

Housecroft

Constable²

2023

Comprehensive Inorganic Chemistry III

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Mixed‐Donor Amido–Siloxo Actinide(IV) Halide and Alkyl Complexes with an Aryl C_ipso Interaction

Abstract: The synthesis and characterisation of a series of new actinide(IV) complexes supported by the mixed-donor amido-amino-siloxo framework [RN(Li)

Cited by 3 publications

References 79 publications

Lanthanides and actinides: Annual survey of their organometallic chemistry covering the year 2014

Lanthanides and actinides: Annual survey of their organometallic chemistry covering the year 2014

Actinides: Amido Complexes

Main group metal coordination chemistry

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Mixed‐Donor Amido–Siloxo Actinide(IV) Halide and Alkyl Complexes with an Aryl Cipso Interaction

Abstract: The synthesis and characterisation of a series of new actinide(IV) complexes supported by the mixed-donor amido-amino-siloxo framework [RN(Li)

Cited by 3 publications

References 79 publications

Lanthanides and actinides: Annual survey of their organometallic chemistry covering the year 2014

Lanthanides and actinides: Annual survey of their organometallic chemistry covering the year 2014

Actinides: Amido Complexes

Main group metal coordination chemistry

Contact Info

Product

Resources

About

Mixed‐Donor Amido–Siloxo Actinide(IV) Halide and Alkyl Complexes with an Aryl C_ipso Interaction