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![Figure S4. Molecular structure of [Sm(Htp)2(μ-BH4)]2 (1-Sm) with selected labelling. Displacement ellipsoids set at 30% probability level and hydrogen atoms apart from those on BH4 -anions are omitted](publication/340976101/figure/fig3/AS:11431281102947147@1669575909592/Figure-S4-Molecular-structure-of-SmHtp2m-BH42-1-Sm-with-selected-labelling.jpg)
Figure S4. Molecular structure of [Sm(Htp)2(μ-BH4)]2 (1-Sm) with selected labelling. Displacement ellipsoids set at 30% probability level and hydrogen atoms apart from those on BH4 -anions are omitted
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![Figure S1. Molecular structure of [La(Htp)2(μ-BH4)]2 (1-La) with...](publication/340976101/figure/fig1/AS:11431281102973331@1669575909489/Figure-S1-Molecular-structure-of-LaHtp2m-BH42-1-La-with-selected-labelling_Q320.jpg)
![Figure S2. Molecular structure of [Ce(Htp)2(μ-BH4)]2 (1-Ce) with...](publication/340976101/figure/fig2/AS:11431281102955624@1669575909521/Figure-S2-Molecular-structure-of-CeHtp2m-BH42-1-Ce-with-selected-labelling_Q320.jpg)
![Figure S4. Molecular structure of [Sm(Htp)2(μ-BH4)]2 (1-Sm) with...](publication/340976101/figure/fig3/AS:11431281102947147@1669575909592/Figure-S4-Molecular-structure-of-SmHtp2m-BH42-1-Sm-with-selected-labelling_Q320.jpg)
![Figure S5. Molecular structure of [{La(Htp)2(μ-BH4)2(K)(DME)2}2] (2-La)...](publication/340976101/figure/fig4/AS:11431281102982670@1669575909668/Figure-S5-Molecular-structure-of-LaHtp2m-BH42KDME22-2-La-with-selected_Q320.jpg)
Organometallic lanthanide (Ln) chemistry is dominated by complexes that contain substituted cyclopentadienyl (CpR) ligands. Closely related phospholyls have received less attention, and although they have proven utility in stabilising low oxidation state Ln complexes the trivalent Ln chemistry of these ligands is limited in comparison. Herein, we s...
Citations
... This can be explained by formation of carbides (considering the typically correct H and N percentages) causing incomplete combustion. 71,72 In some cases, incomplete removal of toluene from the samples could lead to C and H values corresponding to slightly higher toluene content than calculated from the XRD data. IR spectra were registered for KBr pellets, prepared in a glovebox, by means of an FT-801 spectrometer (Simex). ...
The molecular structures of complexes [Sm(Nacnac)I(thf)n] (Nacnac = HC(C(Me)Ndipp)2-, dipp = 2,6-diisopropylphenyl, thf = tetrahydrofuran) depending on the number of thf ligands are studied. The complete removal of thf from a known complex [Sm(Nacnac)I(thf)2] leads to a tetranuclear product [Sm(Nacnac)I]4 (4). The partial removal of thf results in mixtures of dinuclear [Sm2(Nacnac)2I2(thf)] (2), trinuclear [Sm3(Nacnac)3I3(thf)] (3), and tetranuclear [Sm4(Nacnac)4I4(thf)2] (4*) complexes and 4, depending on the conditions. The reaction of solvent-free SmI2 with 1 equiv of K(Nacnac) results mainly in [Sm(Nacnac)2] (1), while the interaction of 4 with certain amounts of thf allows obtaining pure 2 and 3 (with the admixture of 4*). Complex 4* is the exact dimer of 2, and both compounds are stable in solutions. Reactions with 3 and 4 as reductants are studied. 4 is oxidized by I2 to stoichiometrically yield two products, mixed-valent tetranuclear [Sm4(Nacnac)4I5] (5) and binuclear [Sm(Nacnac)I2]2 (6) complexes. In the reaction of 4 with nBu3PTe, a trinuclear complex [Sm3(Nacnac)3(μ-I)3(μ3-E)2] (8, E = I or Te) is formed in small amounts, with the formation of 6 as the second product. 3 serves as a two-electron reductant in the reaction with nBu3PTe to yield a trinuclear complex [Sm3(Nacnac)3I3(μ-Te2)] (7). Complexes 2, 4, 4*, 5, 6, and 8 possess a unique flat SmxIy core of heavy atoms, which is assumed to be a consequence of the Nacnac ligand geometry.
... 463 Monoring complexes, RE(Cp)X 2 , can be particularly challenging to isolate when using halide starting materials, while they are usually readily accessible with borohydride reagents owing to the stabilizing properties of the borohydride ligand and its flexible coordination modes. 464 437 While RE halides can be converted into alkyls and allyls from the reaction with organolithium and Grignard reagents, analogous reactivity of RE borohydrides is not as straightforward. Visseaux and co-workers reacted Nd(BH 4 ) 3 and Sm-(BH 4 ) 3 with Grignard reagents and could not obtain pure products. ...
The number of rare earth (RE) starting materials used in synthesis is staggering, ranging from simple binary metal-halide salts to borohydrides and "designer reagents" such as alkyl and organoaluminate complexes. This review collates the most important starting materials used in RE synthetic chemistry, including essential information on their preparations and uses in modern synthetic methodologies. The review is divided by starting material category and supporting ligands (i.e., metals as synthetic precursors, halides, borohydrides, nitrogen donors, oxygen donors, triflates, and organometallic reagents), and in each section relevant synthetic methodologies and applications are discussed.
... [41] In 2020, Mills and co-workersr eportedaseries of salt metathesis reactions of THF solvates of light Ln III borohydrides with K(Htp) in ar ange of stoichiometries and solvents to afford the polynuclear heteroleptic Ln III phospholyl borohydride complexes [{Ln(h 5 -Htp) 2 (m-BH 4 )} 2 ]( 43-Ln;L n= La, Ce, Nd, Sm) and [Ln(h 5 -Htp) 2 (m-BH 4 ) 2 K(Sol) 2 ] n (44-Ln,L n= La, Ce, Sol = 2 DME, n = 2; 45,Ln= Ce, Sol = Et 2 Oand THF, n = 1). [42] The varying but similarl ocal pseudo-tetrahedral coordinations pheres of {Ln(h 5 -Htp) 2 (BH 4 ) 2 }f ragments in 43-45 weree stablished by single-crystal XRD (LnÀP: 3.089(5) and 3.138(3) , 43-La; 3.058(5) and 3.099(4) , 43-Ce;3 .019(11) and 3.077(6) , 43-Nd;3 .016(6) ...
... .[40][41][42] ...
The f‐block chemistry of phospholyl and arsolyl ligands, heavier p‐block analogues of substituted cyclopentadienyls (CpR, C5R5) where one or more CR groups are replaced by P or As atoms, is less developed than for lighter isoelectronic C5R5 rings. Heterocyclopentadienyl complexes can exhibit properties that complement and contrast with CpR chemistry. Given that there has been renewed interest in phospholyl and arsolyl f‐block chemistry in the last two decades, coinciding with a renaissance in f‐block solution chemistry, a review of this field is timely. Here, the syntheses of all structurally characterised examples of lanthanide and actinide phospholyl and arsolyl complexes to date are covered, including benzannulated derivatives, and together with group 3 complexes for completeness. The physicochemical properties of these complexes are reviewed, with the intention of motivating further research in this field.
New iminophosphonamine Ph2P(HNPbt)(NPbt) (1, HL) bearing chromophore 2-(phen-2'-yl)-1,3-benzothiazole (Pbt) substituents was synthesized and introduced in lanthanide complexes. It was found that salt metathesis reactions between KL (2) generated in situ and LnCl3 lead to the formation of tris-iminophosphonamide complexes [LnL2]L (Ln = Y (3), Sm (4), Gd (5), Dy (6)) regardless of 2/LnCl3 ratio. Compounds 3-6 consist of a cationic fragment [LnL2] + , where the lanthanide atom is surrounded by two rigidly κ 4-coordinated ligands, and an L-anion residing in the outer coordination sphere. Iminophosphonamine 1 shows a rare excitation wavelength-dependent two-band luminescence in the solid state. For compounds containing the deprotonated form, namely potassium salt KL and complexes of Gd and Dy, a single-band luminescence from turquoise to orange was observed. Sm complex reveals a set of a few narrow well-resolved bands corresponding to the f-f transitions against the background of the outer-sphere ligand's emission.
The synthesis of the first half-sandwich complexes based on the cyclononatetraenyl (Cnt = C9H9-) ligand ([LnIII(η9-Cnt)(η3-BH4)2(thf)] (Ln = La, Ce)) is reported. The title compounds were obtained from the reaction of [Ln(BH4)3(thf)3] and [K(Cnt)]. Further solvation of [LnIII(η9-Cnt)(η3-BH4)2(thf)] with tetrahydrofuran (THF) resulted in a reversible decoordination of the Cnt ring and the formation of the ionic species [LnIII(η3-BH4)2(thf)5][Cnt]. Removal of THF from [LaIII(η9-Cnt)(η3-BH4)2(thf)] gave the polymeric compound [LaIII(μ-η2:η2-BH4)2(η3-BH4)(η9-Cnt)]n.
σ-Hydrocarbyl complexes of the form [M(η5-PC4Me4)2(μ-η1:η6-CH2Ph)2K(η6-arene)] (M = La, Ce, Pr, U, Np, Pu; arene = benzene or toluene) were synthesised in one-pot reactions from [MI3(THF)4], or [U(BH4)3(toluene)] (M = U). All complexes were examined by multinuclear (1H, 13C{1H}, 31P{1H}) NMR and UV-vis-NIR spectroscopy, as well as single-crystal X-ray diffraction from which molecular metal-phosphorus bonds for Np and Pu, and a σ-hydrocarbyl metal-carbon bond for Pu, have been structurally authenticated.
Cyclopentadienyls and variants have been the most employed ligands in the organometallic chemistry of the rare earth metals. Their typical, advantageous η⁵-binding mode allows occupation of several metal coordination sites and increases the solubility, while rendering the metal ion quite reactive. Hence, half-sandwich and metallocene complexes have been heavily used in synthesis, catalysis and small molecule activation. Sterically more encumbered Cp-ligands allowed stabilization of unusual electronic ground states, having enormous ramifications on the magnetic properties, primarily for single-molecule magnet design. Although requiring more elaborate synthetic protocols and hence far less common, the heteroatom-substituted phospholyls have also gained recently considerable attention.
We report the preparation of enantiomerically pure constrained geometry complexes (cgc) of the rare‐earth metals bearing a pentadienyl moiety (pdl) derived from the natural product (1R)‐(−)‐myrtenal. The potassium salt 1, [Kpdl*], was treated with ClSiMe2NHtBu, and the resulting pentadiene 2 was deprotonated with the Schlosser‐type base KOtPen/nBuLi (tPen=CMe2(CH2Me)) to yield the dipotassium salt [K2(pdl*SiMe2NtBu)] (3). However, 3 rearranges in THF solution to its isomer 3’ by a 1,3‐H shift, which elongates the bridge between the pdl and SiMe2NtBu moieties by one CH2 unit. This is crucial for the successful formation of various monomeric C1‐ or dimeric C2‐symmetric rare‐earth cgc complexes with additional halide, tetraborohydride, amido and alkyl functionalities. All compounds have been extensively characterised by solid‐state X‐ray diffraction analysis, solution NMR spectroscopy and elemental analyses.
