Abstract
Lanthanoid and actinoid silylamides are versatile starting materials. Herein we show how a simple ligand exchange with tert-butanol leads to the formation of the first trimeric heterobimetallic uranyl(VI)-lanthanoid(III) alkoxide complexes. The μ3 coordination of the endogenous uranyl oxo atom results in a significant elongation of the bond length and a significant deviation from the linear uranyl arrangement.
Highlights
We show how a simple ligand exchange with tert-butanol leads to the formation of the first trimeric heterobimetallic uranyl(VI)–lanthanoid(III) alkoxide complexes
Over the last 15 years the reduction chemistry of uranyl(VI) has seen a renaissance, and the coordination of hetero metal atoms to the uranyl oxo atoms has resulted in a variety of reduced uranium complexes that show catalytic activity,[23] cation-cation interactions (CCIs),[24] thermally, photochemically or chemically reduced uranyl(V) centres and significantly elongated U–O bonds and paramagnetism attributable to the 5f1 state.[25,26,27,28]
Om3QUQO bond lengths are elongated to 1.866–1.902 Å, respectively, when compared to non-oxo-coordinated uranyl compounds (OQUQO 1.78 Å)
Summary
We show how a simple ligand exchange with tert-butanol leads to the formation of the first trimeric heterobimetallic uranyl(VI)–lanthanoid(III) alkoxide complexes. [Li(Et2O)U(OtBu)6] and [KU2(OtBu)9] have been reported, where alkali metals are bridged via OtBu ligands to U(IV) or U(V) centres and none of them contain uranyl (OQUQO2+) units.[13,14] The compound [Zr2(OiPr)9U(C8H8)] prepared from [Zr2(OiPr)9]UI2(THF) by Evans in 2001 is the only known heterobimetallic alkoxide that contains U(III) and a transition metal.[15]
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