Coordination of N-donor ligands to a uranyl(V) beta-diketiminate complex

Inorganic Chemistry
Michael F SchettiniTrevor W Hayton

Abstract

Addition of 2 equiv of AgOTf to [UO(2)(Ar(2)nacnac)Cl](2) (Ar(2)nacnac = {(2,6-Pr(i)(2)C(6)H(3))NC(Me)}(2)CH) in the presence of excess pyridine, followed by addition of Cp(2)Co, generates the uranyl(V) complex UO(2)(Ar(2)nacnac)(py)(2) (2), in moderate yield. Complex 2 has proven to be an excellent precursor for the synthesis of other U(V) complexes. Thus, addition of 2,2'-bipyridine (bipy), 1,10-phenanthroline (phen), TMEDA, or 1-methylimidazole (MeIm) to 2 provides UO(2)(Ar(2)nacnac)(bipy) (3), UO(2)(Ar(2)nacnac)(phen) (4), UO(2)(Ar(2)nacnac)(TMEDA) (5), and UO(2)(Ar(2)nacnac)(MeIm)(2) (6), respectively. Complexes 2-6 have been fully characterized and their structures confirmed by X-ray crystallography. Attempts to form the analogous hexavalent uranyl complexes of bipy, phen, and TMEDA have not been successful. However, reaction of [UO(2)(Ar(2)nacnac)Cl](2) with AgOTf and 2 equiv of MeIm leads to the isolation of [UO(2)(Ar(2)nacnac)(MeIm)(2)][OTf] (7), which has been fully characterized. Attempts to ligate sulfur donor ligands to either the UO(2)(Ar(2)nacnac) or the [UO(2)(Ar(2)nacnac)](+) fragments were unsuccessful.

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Citations

Nov 8, 2012·Chemical Reviews·Matthew B Jones, Andrew J Gaunt
May 7, 2011·Inorganic Chemistry·Jessie L BrownTrevor W Hayton
Dec 12, 2012·Inorganic Chemistry·Merle ArrowsmithIan Mallov
May 14, 2016·Inorganic Chemistry·Elizabeth A PedrickTrevor W Hayton
Nov 8, 2014·Dalton Transactions : an International Journal of Inorganic Chemistry·Mohammad AzamEdwin Kroke
Oct 3, 2018·Dalton Transactions : an International Journal of Inorganic Chemistry·Marissa RinggoldJohn G Brennan
Oct 3, 2012·Dalton Transactions : an International Journal of Inorganic Chemistry·Nicholas E TraviaJaqueline L Kiplinger
May 21, 2013·Dalton Transactions : an International Journal of Inorganic Chemistry·Merle ArrowsmithGabriele Kociok-Köhn
Jan 3, 2018·Dalton Transactions : an International Journal of Inorganic Chemistry·Trevor W Hayton
Jun 5, 2020·Dalton Transactions : an International Journal of Inorganic Chemistry·Michael A BoreenJohn Arnold
Aug 25, 2012·Dalton Transactions : an International Journal of Inorganic Chemistry·Florian DulongThibault Cantat
Jan 27, 2019·Physical Chemistry Chemical Physics : PCCP·Krishnamoorthy Arumugam, Neil A Burton
Aug 23, 2011·Chemical Communications : Chem Comm·Michael F SchettiniTrevor W Hayton
Sep 30, 2017·Dalton Transactions : an International Journal of Inorganic Chemistry·Stephan HohlochJohn Arnold
Jan 14, 2021·Dalton Transactions : an International Journal of Inorganic Chemistry·Rahul AgarwalTamal Kanti Ghosh
Jan 25, 2020·Inorganic Chemistry·Judith RiedhammerDaniel J Mindiola
Jan 15, 2020·Environmental Science & Technology·Gianni F VetteseJonathan R Lloyd

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