A new robust and high-yielding synthesis of the valuable U(III) synthon [U(BH4)3(THF)2] is reported. Reactivity in ligand exchange reactions found to contrast significantly that uranium triiodide. This exemplified by characterization azamacrocyclic complexes, including mononuclear [U(BH4)(L)] dinuclear [Li(THF)4][{U(BH4)}2(μ-BH4)(L(Me))] [Na(THF)4][{U(BH4)}2(μ-BH4)(L(A))(THF)2]. The structures all complexes have been determined single-crystal X-ray diffraction display two U(III)2(BH4)3 motifs.

Actinide complexes of a small-cavity, dipyrrolide macrocycle exhibit unusual bent metallocene-type binding, or bis(arene)-type both at once in di-uranium adduct.

A new dinitrogen adduct of a homoleptic uranium tris(siloxide) complex, [U{OSi(Mes)3}3]2(μ-η2:η2-N2), is reported. Synthesis the 15N-labeled isotopomer and Raman spectroscopy confirm reductive activation N2 to (N2)2– dianion. The 15N NMR shift 15N2-labeled also Crystallographic characterization shows side-on coordinated in either an eclipsed or staggered conformation different crystals. U–N2–U complex stable vacuum high thermal stability, retaining formally reduced at 100 °C. parent...

The diuranium(III) compound [UN''2]2(μ-η(6):η(6)-C6H6) (N''=N(SiMe3)2) has been studied using variable, high-pressure single-crystal X-ray crystallography, and density functional theory . In this compound, the low-coordinate metal cations are coupled through π- δ-symmetric arene overlap show close metal-CH contacts with flexible methyl CH groups of sterically encumbered amido ligands. metal-metal separation decreases increasing pressure, but most significant structural changes to between...

Heteromultimetallic lanthanide (Ln) molecules are used in sensing and imaging, have recently demonstrated Ln to-Ln energy transfer potential as quantum logic processors. However, the selective synthesis of molecular heteromultimetallics is challenging, limiting further investigation their properties applications. For example, redox active ligands mediate f-block reactivity with small applications magnetics homometallic systems, yet not been incorporated into heteromultimetallic complexes....

Deep-blue solutions of Y(2+) formed from Y(NR(2))(3) (R = SiMe(3)) and excess potassium in the presence 18-crown-6 at -45 °C under vacuum diethyl ether react with CO -78 to form colorless crystals (CO)(1-) radical complex, {[(R(2)N)(3)Y(μ-CO)(2)][K(2)(18-crown-6)(2)]}(n), 1. The polymeric structure contains trigonal bipyramidal [(R(2)N)(3)Y(μ-CO)(2)](2-) units axial ligands linked by [K(2)(18-crown-6)(2)](2+) dications. Byproducts such as ynediolate,...

U(III) complexes of the conformationally flexible, small-cavity macrocycle trans-calix[2]benzene[2]pyrrolide (L)2–, [U(L)X] (X = O-2,6-tBu2C6H3, N(SiMe3)2), have been synthesized from [U(L)BH4] and structurally characterized. These show binding center in bis(arene) pocket macrocycle, which flexes to accommodate increase steric bulk X, resulting long U–X bonds ancillary ligands. Oxidation cationic U(IV) complex [U(L)X][B(C6F5)4] BH4) results ligand rearrangement bind smaller, harder cation...

Reduction of heteroleptic Ln( iii ) [Ln(Tp) 2 (OTf)] (Tp = hydrotris(1-pyrazolyl)borate; OTf triflate) with either an Al( i anion or KC 8 yielded the adduct-free ii complexes dimeric 1-Eu [{Eu(Tp)( μ-κ 1 : η 5 -Tp)} ] and monomeric 1-Yb [Yb(Tp) ].

A family of imidazolium salts the type [BnN(CH2CH2CH2RIm)2]·2[Cl] (Bn = CH2Ph; RIm 1-methylimidazole (1a), 1-tert-butylimidazole (1b), 1-benzylimidazole (1c), 1-methylbenzimidazole (1d)), which contain a tertiary amine linking two groups, has been synthesized. These can be deprotonated with Ag2O to generate Ag carbene complexes [{BnN(CH2CH2CH2RIm)2}Ag]·[AgCl2] (RIm (2a), (2b), (2c), (2d)). In solid state 2d exists as an unusual tetramer, consists [Ag2Cl4]2− core bridging Ag(NHC) cations....

Abstract Synthesis of primary lanthanide amides in the bis ‐hydrotris(1‐pyrazolyl)borate ligand environment has been achieved. Salt metathesis [Dy(Tp) 2 (OTf)] 1‐Dy (OTf=CF 3 SO ) with K(N′′) (N′′=N(SiMe toluene yielded [ (silyl)]amide (N′′)] 2‐Dy . Complexes 1‐Ln and 2‐Ln were both used to access amides, where either K(NHAr CF3 (Ar =C 6 H (CF ‐3,5) or protonolysis NAr [Ln(Tp) (NHAr )] 3‐Ln (Ln=Y, Dy). The synthesis parent was also attempted, but 1‐Y NaNH complicated reaction mixtures, from...

Molecular heterobimetallic hydride complexes of lanthanide (Ln) and main-group (MG) metals exhibit chemical properties unique from their monometallic counterparts are highly reactive species, making synthesis isolation challenging. Herein, molecular Ln/Al trihydrides [Ln(Tp)

A family of well-defined Fe(II) complexes the type {BnN(N-CH2(CH2)n-N'-tert-butyl-imidazole-2-ylidene)2}FeCl2 (Bn = benzyl; n 1 (1) or 2 (2)), {BnN(N-CH2(CH2)n-N'-methylbenzimidazole-2-ylidene)2}FeCl2 (n (3) (4)) and {BnN(N-CH2CH2CH2-N'-methylbenzimidazole-2-ylidene)2}FeBr2 (5) has been synthesized. These are rare examples Fe species supported by bidentate NHC ligands. Complexes 2, 3, 4 5 were characterized X-ray crystallography in all cases a distorted tetrahedral geometry is observed...

The first thorium(IV) and uranium(IV) hydrocarbyl complexes of a trans-calix[2]benzene[2]pyrrolide macrocycle can use ligand noninnocence to enable multiple C–H bond activation reactions at the metal. Both alkyl alkynyl supported by L dianion L–2H tetraanion are reported. ThIV UIV monoalkyl-ate [M(L–2H)An(R)] (M = K for R CH2Ph, M Li Me, CH2SiMe3), in which aryl groups metalated, add bonds terminal alkynes across metal ligand, forming AnIV-alkynyl [(L)An(C≡CR′)2] (R′ SiMe3, SiiPr3). This...

We report a robust and modular synthetic route to heterometallic rare earth-transition metal complexes. have used the redox-active bridging ligand 1,10-phenathroline-5,6-dione (pd), which has selective N,N' or O,O' binding sites as template for this route. The coordination complexes [Ln(hfac)3(N,N'-pd)] (Ln = Y [1], Gd [2]; hfac hexafluoroacetylacetonate) were synthesised in high yield. These been fully characterised using range of spectroscopic techniques. Solid state molecular structures 1...

The reaction chemistry of the side-on bound (N2)2–, (N2)3–, and (NO)2– complexes [(R2N)2Y]+ cation (R = SiMe3), namely, [(R2N)2(THF)Y]2(μ-η2:η2-N2), 1, [(R2N)2(THF)Y]2(μ-η2:η2-N2)K, 2, [(R2N)2(THF)Y]2(μ-η2:η2-NO), 3, with oxidizing agents has been explored to search for other (E2)n−, (E N, O), species that can be stabilized by this cation. This led first examples two fundamental classes [(monoanion)2Ln]+ rare earth systems (Ln Sc, Y, lanthanides), oxide tetraphenylborate salt. In addition,...

Molecular heterobimetallic hydride complexes of lanthanides (Ln) and main group (MG) metals exhibit chemical properties unique from their monometallic counterparts are highly reactive species, making synthesis isolation challenging. Herein, molecular Ln/Al trihydrides [Ln(Tp)2(-H)2Al(H)(Nʹʹ)] 2-Ln (Ln = Y, Sm, Dy, Yb; Tp hydrotris(1-pyrazolyl)borate; Nʹʹ N(SiMe3)2) have been synthesised by facile insertion aminoalane [Me3N•AlH3] into the Ln–N amide bonds [Ln(Tp)2(Nʹʹ)] 1-Ln. Thus, providing...

The activation and functionalisation of carbon dioxide by bis-tris(pyrazolyl)borate-supported divalent samarium trivalent lanthanide silylamide complexes have been reported.

Abstract The diuranium(III) compound [UN′′ 2 ] (μ‐η 6 :η ‐C H ) (N′′=N(SiMe 3 has been studied using variable, high‐pressure single‐crystal X‐ray crystallography, and density functional theory . In this compound, the low‐coordinate metal cations are coupled through π‐ δ‐symmetric arene overlap show close metalCH contacts with flexible methyl CH groups of sterically encumbered amido ligands. metal–metal separation decreases increasing pressure, but most significant structural changes to...

The effect of the neutral donor ligand, L, on Ln2N2 core in (N═N)2– complexes, [A2(L)Ln]2(μ-η2:η2-N2) (Ln = Sc, Y, lanthanide; A monoanion; L ligand), is unknown since all crystallographically characterized examples were obtained with tetrahydrofuran (THF). To explore variation displacement reactions between {[(Me3Si)2N]2(THF)Y}2(μ-η2:η2-N2), 1, and benzonitrile, pyridine (py), 4-dimethylaminopyridine (DMAP), triphenylphosphine oxide, trimethylamine N-oxide investigated. THF displaced by...