41836-21-9

Usage

Uses

Used in Chemical Synthesis:
Tris[N,N-bis(trimethylsilyl)amide]cerium(III) is used as a reactant for the synthesis of various compounds, including amidocerium(IV) oxides, sterically encumbered N-heterocyclic carbene ligands, and lanthanide imidodiphosphinate complexes with electroluminescent properties. It is also used in the synthesis of lanthanide complexes of an oxazoline-phenoxide hybrid chelate.
Used in One-electron Oxidation:
Tris[N,N-bis(trimethylsily)amide]cerium(III) is utilized as a reactant for one-electron oxidation processes to produce tetravalent cerium compounds. This application is significant in the development of new materials and compounds with unique properties.
Used in Addition-Elimination Reactions:
Tris[N,N-bis(trimethylsilyl)amide]cerium(III) is also used as a reactant in addition-elimination reactions across the M-C bond of metal N-heterocyclic carbenes. This application highlights its versatility in facilitating chemical reactions and contributing to the synthesis of novel materials.

InChI:InChI=1/3C6H18NSi2.Ce/c3*1-8(2,3)7-9(4,5)6;/h3*1-6H3;/q3*-1;+3

Upstream product

• 40949-94-8 potassium hexamethylsilazane 
• 1070-89-9 sodium hexamethyldisilazane 
• 7790-86-5 cerium chloride 
• 4039-32-1 lithium hexamethyldisilazane 
• 76089-77-5 cerium triflate 

Downstream Products

• 113034-77-8 cerium(III) 2,6-di-t-butyl-phenoxide 
• 113034-78-9 Ce(2,6-t-(C₄H₉)2-4-CH₃-C₆H₂O)3 
• 454470-87-2 tris(bis(trimethylsilyl)amido)(cyclohexylisocyanide)2Ce(III) 
• 1260370-62-4 (Ce(2,6-diallyl-4-methylphenolato)2(μ-2,6-diallyl-4-methylphenolato))2 
• 1626423-31-1 [Ce{N(SiMe₃)₂}₃(1,4-benzenediolato)_0.5]₂ 
• 1605281-59-1 tetrakis(hydroxamate) cerium(IV) 
• 1445605-43-5 [Na(diethyl ether)₄][Ce^III(decafluorodiphenylamide)₄] 

Relevant academic research and scientific papers

Lanthanide(III) Di- and tetra-nuclear complexes supported by a chelating tripodal tris(amidate) ligand

Syntheses, structural, and spectroscopic characterization of multinuclear tris(amidate) lanthanide complexes is described. Addition of K3[N(o-PhNC(O)tBu)3] to LnX3 (LnX3 = LaBr3, CeI3

Synthesis, solid state structure, and solution behaviour of the lighter lanthanide bis(trimethylsilyl)amido chlorides, [Ln{N(SiMe3)2}2(THF)(μ- Cl)]2 (Ln = Ce, Nd)

The synthesis of [Ln{N(SiMe3)2}2(THF)(μ-Cl)]2 (Ln = Ce, 1; Nd, 2) by reaction of sodium bis(trimethylsilyl)amide (2 equiv.) with LnCl3 is reported. The same complexes were also isolated from the ligand redistribution reactions of Ln[N(SiMe3)2]3 and LnCl3 (2:1 ratio) in THF at 80°C. The crystal structure of 2, determined by X-ray diffraction, revealed a centrosymmetric dimer with bridging chlorides and pentacoordinate metal centres. 1H NMR studies show that the solid state structure is not maintained in solution. NMR evidence for the presence of Ln[N(SiMe3)2]3 and two other bis(trimethylsilyl)amide containing species, presumably Ln[N(SiMe3)2]Cl2(THF)(x) and Ln[N(SiMe3)2]2Cl(THF)(y), is presented.

A structural investigation of heteroleptic lanthanide substituted cyclopentadienyl complexes

The substituted cyclopentadienyl group 1 transfer agents KCp′′, KCp′′′ and KCptt (Cp′′ = {C5H3(SiMe3)2-1,3}-; Cp′′′ = {C5H2(SiMe3)3-1,2,4}-; Cptt = {C5H3(tBu)2-1,3}-) were prepared by modification of established procedures and the structure of [K(Cp′′)(THF)]∞·THF (1) was obtained. KCp′′ and KCptt were reacted variously with [Ln(I)3(THF)4] (Ln = La, Ce) in 2-1 stoichiometries to afford monomeric [La(Cp′′)2(I)(THF)] (2a·THF) and the dimeric complexes [La(Cp′′)2(μ-I)]2 (2a), [Ce(Cp′′)2(μ-I)]2 (2b) and [Ce(Cptt)2(μ-I)]2 (3). KCp′′′ was reacted with [Ce(I)3(THF)4] to afford the mono-ring complex [Ce(Cp′′′)(I)2(THF)2] (4), regardless of the stoichiometric ratio of the reagents. Complex 4 was reacted with [KN(SiMe3)2] to yield [Ce(Cp′′′)2(I)(THF)] (5), [Ce(Cp′′′){N(SiMe3)2}2] (6) and [Ce{N(SiMe3)2}3] by ligand scrambling. Complexes 1-6 have all been structurally authenticated and are variously characterised by other physical methods.

The synthesis, structures and polymorphism of the dimeric trivalent rare-earth 3,5-dimethylpyrazolate complexes [Ln(Me2pz) 3(thf)]2

A variety of rare-earth 3,5-dimethylpyrazolate (Me2pz) complexes have been synthesised by (i) the direct reaction of Hg-activated metal with Me2pzH as a pro-ligand at elevated temperatures, (ii) by redox transmetalation/protolysis with the lanthanoid element, Hg(C6F 5)2, and Me2pzH, and (iii) by protolysis of tris[bis(trimethylsilyl)amido]cerium(III) with Me2pzH. Each product, upon crystallisation from tetrahydrofuran (thf), formed a dimeric complex, [Ln(Me2pz)3(thf)]2 (Ln = La, Ce, Pr, Nd, Ho, Yb, or Lu). Despite the common formulation, two completely different structures were observed in two distinct crystallographic domains of existence , together presumptively spanning the gamut of Ln and Y. For the larger rare-earth ions (La-Pr), there are two terminal η2-Me 2pz ligands and one thf donor on each Ln atom, with the metal atoms being linked by a pair of bridging pyrazolate ligands of an uncommon type (η2:η5), resulting in formal ten-coordination. A Me2pzH complex [Ce(Me2pz)3(Me2pzH)], although not isomorphous, has a similar structure. For the smaller rare-earth elements (Nd-Lu), the bridging is entirely different, with two μ-κ1(N):κ1(N) pyrazolate and two unusual bridging thf ligands. Each Ln atom also has two chelating Me2pz ligands, resulting in formal eight-coordination. Crystallisation of [Nd(Me 2pz)3(thf)]2 from pyridine yields monomeric, nine-coordinate [Nd(Me2pz)3(pyridine)3] with only chelating Me2pz ligands. Contrasting structures and bridging Me2pz groups for Ln = La-Pr and Ln = Nd-Lu are described. Copyright

Diethyl ether adducts of trivalent lanthanide iodides

The synthesis and structural characterization of the first molecular complexes of lanthanide iodides supported by the weak-base, diethyl ether, are reported. Single-crystal diffraction studies reveal a conserved [LnI3(mer-Et2O)3

Small-Scale Metal-Based Syntheses of Lanthanide Iodide, Amide, and Cyclopentadienyl Complexes as Analogues for Transuranic Reactions

Small-scale reactions of the Pu analogues La, Ce, and Nd have been explored in order to optimize reaction conditions for milligram scale reactions of radioactive plutonium starting from the metal. Oxidation of these lanthanide metals with iodine in ether

Synthesis, characterization, and utility of trifluoroacetic acid lanthanide precursors for production of varied phase fluorinated lanthanide nanomaterials

The synthesis of a series of lanthanide trifluoroacetic acid (H-TFA) derivatives which contain only the TFA and its conjugate acid has been developed. From the reaction of Ln(N(SiMe3)2)3 with an excess amount of H-TFA, the products were identified as: [Ln(μ-TFA)3(H-TFA)2]n (Ln?=?Y, Ce, Sm, Eu, Gd, Tb, Dy), [Ln(μ-TFA)3(μ-H-TFA)]n·solv (Ln·solv?=?Pr·2 H-TFA, H3O+, Ho·2py, Er·py, Yb·py, H-TFA), 3[H][(TFA)La(μ-TFA)3La(TFA)(μ-TFA)2(μc-TFA)2]n ?(H2O) ?(H2O, H-TFA) (La·?(H2O) ?(H2O, H-TFA)), [(k2-TFA)Nd(μ-TFA)3]n·H-py+ (Nd·H-py+), [(py)2Tm(μ-TFA)3]n (Tm), or [Lu(μ-TFA)4Lu(μ-TFA)3·H3O+]n (Lu·H3O+). The majority of samples formed long chain polymers with 3 or 4 μ-TFA ligands. Tm was isolated with py coordinated to the metal, whereas Ho, Er, and Yb were isolated with py located within the lattice. Select samples from this set of compounds were used to generate nanomaterials under solvothermal (SOLVO) conditions using pyridine (py) or octylamine at 185?°C for 24?h. The SOLVO products were isolated as: (i) from py: La – fluocerite (LaF3, PDF 98-000-0214, R?=?9.64%, 35(0) nm), Tb – terbium fluoride (TbF3, PDF 00-037-1487, R?=?4.76%, 21(2) nm), Lu lutetium oxy fluoride (LuOF, PDF 00-052-0779, R?=?8.24%, 8(2) nm); (ii) from octylamine: La – fluocerite/lanthanum oxide carbonate (LaF3, PDF 98-000-0214, R?=?7.47%, 5(0) nm; La2O2(CO3), PDF 01-070-5539, R?=?12.32%, 12(0) nm), Tb – terbium oxy fluoride (TbOF, PDF 00-008-0230, R?=?7.01%, 5(0) nm); Lu – lutetium oxide (Lu2O3, PDF 00-012-0728, R?=?6.52%, 6(1) nm).

Cerium(III/IV) formamidinate chemistry, and a stable cerium(IV) diolate

Four new cerium(III) formamidinate complexes comprising [Ce(p-TolForm) 3], [Ce(DFForm)3(thf)2], [Ce(DFForm) 3], and [Ce(EtForm)3] were synthesized by protonolysis reactions using [Ce{N(SiMe3)2}3] and formamidines of varying functionality, namely N,N′-bis(4-methylphenyl) formamidine (p-TolFormH), N,N′-bis(2,6-difluorophenyl)formamidine (DFFormH), and the sterically more demanding N,N′-bis(2,6-diethylphenyl) formamidine (EtFormH). The bimetallic cerium lithium complex [LiCe(DFForm) 4] was synthesized by treating a mixture of [Ce{N(SiHMe 2)2}3(thf)2] and [Li{N(SiHMe 2)2}] with four equivalents of DFFormH in toluene. Oxidation of the trivalent cerium(III) formamidinate complexes by trityl chloride (Ph3CCl) caused dramatic color changes, although the cerium(IV) species appeared transient and reformed cerium(III) complexes and N′-trityl-N,N′-diarylformamidines shortly after oxidation. The first structurally characterized homoleptic cerium(IV) formamidinate complex [Ce(p-TolForm)4] was obtained through a protonolysis reaction between [Ce{N(SiHMe2)2}4] and four equivalents of p-TolFormH. [Ce{N(SiHMe2)2}4] was also treated with DFFormH and EtFormH, but the resulting cerium(IV) complexes decomposed before isolation was possible. The new cerium(IV) silylamide complex [Ce{N(SiMe3)2}3(bda)0.5] 2 (bda=1,4-benzenediolato) was synthesized by treatment of [Ce{N(SiMe3)2}3] with half an equivalent of 1,4-benzoquinone, and showed remarkable resistance towards protonolysis or reduction. Figure ate: The reaction of ate complex [Li(thf)Ce{N(SiHMe 2)2}4 with C2Cl6 gives straightforward access to the homoleptic complex [Ce{N(SiHMe2) 2}4], which engages in protonolysis reactions (see scheme) with formamidines to afford the first CeIV formamidinate species [Ce(p-TolForm)4] (p-TolForm=N,N′-bis(4-methylphenyl) formamidinato).

The synthesis, structures and polymorphism of the dimeric trivalent rare-earth 3,5-dimethylpyrazolate complexes [Ln(Me2pz)3(thf)]2

A variety of rare-earth 3,5-dimethylpyrazolate (Me2pz) complexes have been synthesised by (i) the direct reaction of Hg-activated metal with Me2pzH as a pro-ligand at elevated temperatures, (ii) by redox transmetalation/protolysis with the lanthanoid element, Hg(C6F5)2, and Me2pzH, and (iii) by protolysis of tris[bis(trimethylsilyl)amido]cerium(III) with Me2pzH. Each product, upon crystallisation from tetrahydrofuran (thf), formed a dimeric complex, [Ln(Me2pz)3(thf)]2 (Ln = La, Ce, Pr, Nd, Ho, Yb, or Lu). Despite the common formulation, two completely different structures were observed in two distinct crystallographic domains of existence , together presumptively spanning the gamut of Ln and Y. For the larger rare-earth ions (La-Pr), there are two terminal η2-Me2pz ligands and one thf donor on each Ln atom, with the metal atoms being linked by a pair of bridging pyrazolate ligands of an uncommon type (η2:η5), resulting in formal ten-coordination. A Me2pzH complex [Ce(Me2pz)3(Me2pzH)], although not isomorphous, has a similar structure. For the smaller rare-earth elements (Nd-Lu), the bridging is entirely different, with two μ-κ1(N):κ1(N) pyrazolate and two unusual bridging thf ligands. Each Ln atom also has two chelating Me2pz ligands, resulting in formal eight-coordination. Crystallisation of [Nd(Me2pz)3(thf)]2 from pyridine yields monomeric, nine-coordinate [Nd(Me2pz)3(pyridine)3] with only chelating Me2pz ligands. Contrasting structures and bridging Me2pz groups for Ln = La-Pr and Ln = Nd-Lu are described.

Cerium(III) dialkyl dithiocarbamates from [Ce{N(SiMe3)2}3] and tetraalkylthiuram disulfides, and [Ce(κ2-S2 CNEt2)4] from the CeIII precursor; TbIII and NdIII analogues

The synthesis and characterisation of the first neutral cerium dialkyl dithiocarbamate complexes, using a novel oxidative displacement of the amido ligands of [Ce{N (SiMe3)2}3] by tetraalkylthiuram disulfides [R2NC(S)S]2 (R = Me, Et) in thf solution, are reported. In the absence of other donors, the complexes [Ce(κ2-S2CNMe2)3 (thf)2] 2 and Ce(κ2-S2CNEt2)3 3 were obtained. The addition of a polypyridyl ligand allowed easy access to a range of complexes of general formula [Ce(κ2-S2 CNR2)3(L∩L)][R = Me and L∩L = 2,2′-bipy (4), or 4,7-diphenyl-1,10-phenanthroline (6); or R = Et and L∩L = 2,2′-bipy (5)]. Brief exposure of the Ce(III) dithiocarbamate 3 to oxygen gas afforded in high yield the diamagnetic, crystalline Ce(IV) dithiocarbamate [Ce(κ2-S2CNEt2)4] 7. The neodymium (8) and terbium (10) complexes, isoleptic with 2, were prepared from the appropriate 4f metal (Ln) bis(trimethylsilyl)amide [Ln{N(SiMe3)2}3] [Ln = Nd or Tb (9)] and [Me2NC(S)S]2. The structures of the crystalline complexes 2, 4, 6, 7, 9 and 10 have been determined by X-ray crystallography. Some evidence has been obtained for the formation of the cerium(IV) complex Ce{N(SiMe3)2}2 (κ2-S2CNMe2)2. The cerium(IV) complex 7 has the metal coordinated to eight sulfur atoms of four planar chelating S2CNC2 moieties and its geometry is intermediate between dodecahedral and square prismatic; the mean Ce-S bond length of 2.803 A in 7 compares with the 2.950 A in the Ce(III) complex 2.