Issue 4, 2023

A versatile strategy for the formation of hydride-bridged actinide–iridium multimetallics

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)3IrCp*}4 (1) and Th{[(μ-H2)(H)IrCp*]2[(μ-H)3IrCp*]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[(μ2-H3)IrCp*]2[(μ3-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.

Graphical abstract: A versatile strategy for the formation of hydride-bridged actinide–iridium multimetallics

Supplementary files

Article information

Article type
Edge Article
Submitted
02 Sep 2022
Accepted
18 Dec 2022
First published
19 Dec 2022
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2023,14, 861-868

A versatile strategy for the formation of hydride-bridged actinide–iridium multimetallics

C. Z. Ye, I. Del Rosal, M. A. Boreen, E. T. Ouellette, D. R. Russo, L. Maron, J. Arnold and C. Camp, Chem. Sci., 2023, 14, 861 DOI: 10.1039/D2SC04903A

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