A versatile strategy for the formation of hydride-bridged actinide–iridium multimetallics. Issue 4 (3rd January 2023)

• Record Type: Journal Article
• Authors: Ye, Christopher Z.; Del Rosal, Iker; Boreen, Michael A.; Ouellette, Erik T.; Russo, Dominic R.; Maron, Laurent; Arnold, John; Camp, Clément
• Is Part Of: Chemical science. Volume 14:Issue 4(2023)
• Page Start: 861
• Page End: 868
• Publication Date: 2023-01-03
• Subjects: Chemistry -- Periodicals; 540.5
• DOI: 10.1039/d2sc04903a
• Languages: English
• ISSNs: 2041-6520

Abstract

Abstract : Uranium- and thorium-iridium multimetallic species with unprecedented actinide–iridium interactions are prepared via salt-elimination reactions between U/Th halides and K[IrCp*H3 ]. Abstract : Reaction of the potassium pentamethylcyclopentadienyl iridate tris-hydride K[IrCp*H3 ] with UCl4 and ThCl4 (DME)2 led to the complete replacement of the halide ligands to generate multimetallic complexes U{(μ-H)3 IrCp*}4 (1 ) and Th{[(μ-H2 )(H)IrCp*]2 [(μ-H)3 IrCp*]2 } (2 ), respectively. These analogues feature a significant discrepancy in hydride bonding modes; 1 contains twelve bridging hydrides while 2 contains ten bridging hydrides and two terminal, Ir-bound hydrides. Use of a U(iii ) starting material, UI3 (1, 4-dioxane)1.5, resulted in the octanuclear complex {U[(μ 2 -H3 )IrCp*]2 [(μ 3 -H2 )IrCp*]}2 (3 ). Computational studies indicate significant bonding character between U/Th and Ir in 1 and 2, with f-orbital involvement in the singly-occupied molecular orbitals of the uranium species 1 . In addition, these studies attribute the variation in hydride bonding between 1 and 2 to differences in dispersion effects.