Cooperative dihydrogen activation with unsupported uranium-metal bonds and characterization of a terminal U(iv)
Robert J Ward1, Pokpong Rungthanaphatsophon1, Patrick Huang2
1Department of Chemistry, University of Missouri Columbia MO 65211 USA walenskyj@missouri.edu.
Abstract:
Cooperative chemistry between two or more metal centres can show enhanced reactivity compared to the monometallic fragments. Given the paucity of actinide-metal bonds, especially those with group 13, we targeted uranium(iii)-aluminum(i) and -gallium(i) complexes as we envisioned the low-valent oxidation state of both metals would lead to novel, cooperative reactivity. Herein, we report the molecular structure of [(C5Me5)2(MesO)U-E(C5Me5)], E = Al, Ga, Mes = 2,4,6-Me3C6H2, and their reactivity with dihydrogen. The reaction of H2 with the U(iii)-Al(i) complex affords a trihydroaluminate complex, [(C5Me5)2(MesO)U(μ2-(H)3)-Al(C5Me5)] through a formal three-electron metal-based reduction, with concomitant formation of a terminal U(iv) hydride, [(C5Me5)2(MesO)U(H)]. Noteworthy is that neither U(iii) complexes nor [(C5Me5)Al]4 are capable of reducing dihydrogen on their own. To make the terminal hydride in higher yields, the reaction of [(C5Me5)2(MesO)U(THF)] with half an equivalent of diethylzinc generates [(C5Me5)2(MesO)U(CH2CH3)] or treatment of [(C5Me5)2U(i)(Me)] with KOMes forms [(C5Me5)2(MesO)U(CH3)], which followed by hydrogenation with either complex cleanly affords [(C5Me5)2(MesO)U(H)]. All complexes have been characterized by spectroscopic and structural methods and are rare examples of cooperative chemistry in f element chemistry, dihydrogen activation, and stable, terminal ethyl and hydride compounds with an f element.
More Related Videos
08:40Synthesis of Metal Nanoparticles Supported on Carbon Nanotube with Doped Co and N Atoms and its Catalytic Applications in Hydrogen Production
Published on: December 6, 2021
10:52Line Shape Analysis of Dynamic NMR Spectra for Characterizing Coordination Sphere Rearrangements at a Chiral Rhenium Polyhydride Complex
Published on: July 27, 2022
Related Concept Videos
03:08Hydroboration-Oxidation of Alkenes
01:26Radical Substitution: Hydrogenolysis of Alkyl Halides with Tributyltin Hydride
The bonds formed in this reaction are stronger than the bonds broken, making it energetically favorable. The reaction follows a radical chain mechanism similar to radical halogenation...
01:20Aldehydes and Ketones with Water: Hydrate Formation
The formation of hydrates is a reversible reaction. Hydrate formation is influenced by steric and electronic factors accompanying the alkyl substituents on the carbonyl group: The rate of hydrate formation increases with a decrease in the number of alkyl groups attached to the carbonyl carbon. Hence,...
00:54Radical Formation: Homolysis
02:47Alkynes to Aldehydes and Ketones: Hydroboration-Oxidation
One of the convenient methods for the preparation of aldehydes and ketones is via hydration of alkynes. Hydroboration-oxidation of alkynes is an indirect hydration reaction in which an alkyne is treated with borane followed by oxidation with alkaline peroxide to form an enol that rapidly converts into an aldehyde or a ketone. Terminal alkynes form aldehydes, whereas internal alkynes give ketones as the final product.
02:36Regioselectivity and Stereochemistry of Hydroboration
Hydroboration proceeds in a concerted fashion with the attack of borane on the π bond, giving a cyclic four-centered transition state. The –BH2 group is bonded to the less substituted carbon and –H to the more substituted carbon. The concerted nature requires the simultaneous addition of –H and –BH2 across the same face of the alkene giving syn...