Recent advances in the coordination chemistry of cerium(IV) complexes

A Combined Experimental and Theoretical Study of the Versatile Reactivity of an Oxocerium(IV) Complex: Concerted Versus Reductive Addition

“…Oxo ligands are well documented in lanthanide chemistry, but invariably bind in a bridging rather than terminal mode, unlike the well‐known actinide terminal oxo complexes . To date, the four cerium(IV) oxo complexes reported by some of us, and others, are the only examples of lanthanide terminal oxo complexes . Recently, we reported the isolation of the first Ce IV terminal oxo complex [(L OEt ) 2 Ce(=O)(H 2 O)] ⋅ MeC(O)NH 2 ( 1 ; L OEt − =[Co(η 5 ‐C 5 H 5 ){P(O)(OEt) 2 } 3 ] − ) (Scheme ) .…”

“…Recently, we reported the isolation of the first Ce IV terminal oxo complex [(L OEt ) 2 Ce(=O)(H 2 O)] ⋅ MeC(O)NH 2 ( 1 ; L OEt − =[Co(η 5 ‐C 5 H 5 ){P(O)(OEt) 2 } 3 ] − ) (Scheme ) . This major breakthrough in cerium chemistry has been rapidly developed by excellent contributions from others, for example, in the synthesis of the first cerium(IV)–imido complexes . The initial reactivity studies of the oxocerium complex 1 are intriguing in their variation: we have found both a classical 1,2‐insertion without change of the Ce oxidation state ([2π+2π]‐type metathesis) and reductive insertion (Scheme ) .…”

“…[6] To date, the four cerium(IV)o xo complexes reported by some of us, and others, are the only examples of lanthanidet erminal oxo complexes. [7,8] Recently,w er eported the isolation of the first Ce IV…”

“…This major breakthroughi nc erium chemistry has been rapidlyd eveloped by excellent contributions from others, [8] fore xample, in the synthesis of the first cerium(IV)-imidocomplexes. [7e, 9] The initial reactivity studies of the oxoceriumc omplex 1 are intriguingi n their variation:w eh ave found both ac lassical 1,2-insertion without change of the Ce oxidation state ([2p + 2p]-type metathesis)a nd reductivei nsertion (Scheme 1).…”

Crystallization Pathways of Cerium(IV) Phosphates Under Hydrothermal Conditions: A Search for New Phases with a Tunnel Structure

“…The crystallographic data and properties of cerium(III) phosphates – monazite ( P 2 1 / n ) and rhabdophane ( P 6 2 22) – have been thoroughly studied . Surprisingly, information on cerium(IV) phosphates is extremely scarce, despite their long history since the middle of the 20 th century and rich ceric coordination chemistry …”