Cerium tetrakis(diisopropylamide) – a useful precursor for cerium(iv) chemistry

Abstract

Homoleptic cerium(IV) diisopropylamide was synthesized via oxidation of ate complex Ce(NiPr2)4Li(thf) with trityl chloride or hexachloroethane. Due to its ready accessibility, and high pKa value of the proligand HNiPr2, Ce(NiPr2)4 features a promising candidate for protonolysis reactions, as shown for the synthesis of dimeric cerium(IV) tetrakis(1,1,3,3-N,N,N',N'-tetramethylguanidinate).

A Macrocyclic Chelator That Selectively Binds Ln4+ over Ln3+ by a Factor of 1029

“…[55][56] Molecular cerium compounds are usually stabilized in the 4+ formal oxidation state by halides 57 and hard, oxygen donor ligands such as alkoxides [58][59][60][61][62][63][64][65][66][67] and acetylacetonates. [68][69] Many "non-classical" tetravalent cerium molecules have also been prepared, including organometallic compounds, [70][71][72] amide, 65,70,[73][74][75][76][77][78] porphyrins [79][80][81][82][83] and a variety of other multidentate N-donor ligands. [84][85][86][87][88][89][90][91] Among these, the lanthanide sandwich molecule cerocene, (C8H8)2Ce, [92][93][94][95][96][97][98][99][100]…”

Reduction of a Cerium(III) Siloxide Complex To Afford a Quadruple‐Decker Arene‐Bridged Cerium(II) Sandwich

“…The hard nature of the tris( tert ‐butoxy)siloxide ligand makes it a good candidate for the synthesis of a homoleptic complex of cerium(IV) . Treatment of complex 1 with 0.5 equiv of C 2 Cl 6 (a reagent used for the synthesis of Ce IV amides) did not lead to oxidation of 1 .…”

Reactivity of Trivalent Ate Complex (thf)LiCe[N(SiHMe2)2]4 toward 1,1,3,3‐N,N,N′,N′‐Tetramethylguanidine

“…L TMG was further reported in main group metal chemistry as an intermediate in the [Al(NMe 2 ) 3 ] 2 ‐catalyzed formation of hexamethylmelamine using dimethylcyanamide as a starting material . In 2014, we described the synthesis of the first homoleptic TMG complex of the lanthanide series, tetravalent cerium Ce 2 (TMG) 8 . For the ceric derivative, formation of L TMG was not observed, even when an excess of HTMG was employed.…”