Controlled synthesis of lanthanide–lithium inverse crown ether complexes

Lu, Xinhua; Ma, Mengtao; Yao, Yingming; Zhang, Yong; Shen, Qi

doi:10.1016/j.inoche.2010.09.013

Cited by 9 publications

(3 citation statements)

References 10 publications

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“…A further Mn(II) ICE complex was isolated using 2,2,6,6-tetramethylpiperidide as the amido anion . A few other ICE complexes exist for s- and p-block − metals and one f-block ytterbium ICE complex . The complex 5 , however, is the first example for nickel (Scheme ).…”

Section: Resultsmentioning

confidence: 99%

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Ni(I) and Ni(II) Bis(trimethylsilyl)amides Obtained in Pursuit of the Elusive Structure of Ni{N(SiMe₃)₂}₂

McLoughlin,

Witt,

Power

2024

Inorg. Chem.

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Salt metathesis routes to five new −N(SiMe 3 ) 2 nickel derivatives were studied to illuminate their mode of formation, structures, and spectroscopy. The reaction between NiI 2 and K{N(SiMe 3 ) 2 } afforded the Ni(II) and Ni(I) complexes 4) was obtained by using NiCl 2 (DME) (DME = 1,2-dimethoxyethane) as the nickel source rather than NiI 2 . The isolation of the Ni(I) complexes 2 and 4 highlights the tendency for K{N(SiMe 3 ) 2 } to function as a reducing agent. Introduction of adventitious O 2 to solutions ofComplex 5 is the first ICE complex of nickel and is one of four known ICE complexes for the 3d metals. The experimental results indicate that the reduced Ni(I) bis(trimethylsilyl)amides are relatively easily generated, whereas Ni(III) derivatives that might be expected from a disproportionation of a Ni(II) derivative are apparently not yet isolable by the above routes. Overall, the new species crystallize readily from the reaction mixtures, but under ambient conditions, they begin to decompose as solids within ca. 24 h, which hinders their characterization.■ EXPERIMENTAL SECTION General Considerations. All manipulations were carried out under anaerobic and anhydrous conditions by using standard Schlenk techniques or in a Vacuum Atmospheres OMNI-Lab drybox under an

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Section: Resultsmentioning

confidence: 99%

“… 27 A few other ICE complexes exist for s- and p-block 30 − 34 metals and one f-block ytterbium ICE complex. 35 The complex 5 , however, is the first example for nickel ( Scheme 2 ).…”

Section: Resultsmentioning

confidence: 99%

Ni(I) and Ni(II) Bis(trimethylsilyl)amides Obtained in Pursuit of the Elusive Structure of Ni{N(SiMe₃)₂}₂

McLoughlin,

Witt,

Power

2024

Inorg. Chem.

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“…Accordingly, lithium was examined as a reductant in LnA 3 /M reactions to determine if it offers any advantages over sodium or potassium in eqs and . Due to its small size, lithium has the capacity to become incorporated into organometallic complexes by coordinating to cyclopentadienyl, amide, or aryloxide ligands. − This could produce complexes with different reactivity compared to the [K(crypt)][Cp′ 3 Ln], 1-Ln , and [K(crypt)][Cp″ 3 Ln] series of complexes in eq , which are typically isolated with [alkali metal (chelate)] 1+ countercations. To explore these options, reductions with lithium were examined both in the presence and the absence of chelators.…”

Section: Introductionmentioning

confidence: 99%

Utility of Lithium in Rare-Earth Metal Reduction Reactions to Form Nontraditional Ln²⁺ Complexes and Unusual [Li(2.2.2-cryptand)]¹⁺ Cations

2018

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The utility of lithium compared to other alkali metals in generating Ln rare-earth metal complexes via reduction of Ln precursors in reactions abbreviated as LnA/M (Ln = rare-earth metal; A = anionic ligand; M = alkali metal) is described. Lithium reduction of Cp'Ln (Cp' = CHSiMe; Ln = Y, Tb, Dy, Ho) under Ar in the presence of 2.2.2-cryptand (crypt) forms new examples of crystallographically characterizable Ln complexes of these metals, [Li(crypt)][Cp'Ln]. In each complex, lithium is found in an NO donor atom coordination geometry that is unusual for the cryptand ligand. Magnetic susceptibility data on these new examples of nontraditional divalent lanthanide complexes are consistent with 4f5d electronic configurations. The Dy and Ho complexes have exceptionally high single-ion magnetic moments, 11.35 and 11.67 μ, respectively. Lithium reduction of Cp'Y under N at -35 °C forms the Y complex (Cp'Y), which reduces dinitrogen upon warming to room temperature to generate the (N) complex [Cp'Y(THF)](μ-η:η-N). These results provide insight on the factors that lead to reduced dinitrogen complexes and/or stable divalent lanthanide complexes as a function of the specific reducing agent and conditions.

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New Homoleptic Rare‐Earth Metal Complexes Comprising the Unsymmetrically Substituted Amidinate Ligand [MeC(NEt)(NtBu)]^–

Harmgarth

Liebing

Hilfert

et al. 2019

Zeitschrift anorg allge chemie

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New homoleptic complexes of selected rare-earth elements containing the unsymmetrically substituted amidinate ligand [MeC(NEt)(NtBu)] -[= (L) -] were synthesized and fully characterized. Treatment of in situ-prepared Li(L) (1) with anhydrous lanthanide(III) chlorides, LnCl 3 (Ln = Sc, La, Ce, Ho), afforded three different types of amidinate complexes depending on the ionic radius of the central metal atom. The large La 3+ formed the octa-coordinate DME solvate La(L) 3 (DME) (2). Using Ce 3+ , the octa-coordinate "ate" complex Li(THF)[Ce(L) 4 ] (3) was formed. Depending on the crystallization 1101 conditions, compound 3 could be crystallized in two modifications differing in the coordination environment around Li. In the case of the smaller Sc 3+ and Ho 3+ ions, six-coordinate homoleptic Sc(L) 3 (4) and Ho(L) 3 (5) were isolated. The title compounds were fully characterized by spectroscopic and analytical methods as well as single-crystal X-ray diffraction. With Ln = La and Ce, several by-products incorporating lithium, chlorine and/or oxygen were also isolated and structurally characterized.

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Controlled synthesis of lanthanide–lithium inverse crown ether complexes

Cited by 9 publications

References 10 publications

Ni(I) and Ni(II) Bis(trimethylsilyl)amides Obtained in Pursuit of the Elusive Structure of Ni{N(SiMe₃)₂}₂

Ni(I) and Ni(II) Bis(trimethylsilyl)amides Obtained in Pursuit of the Elusive Structure of Ni{N(SiMe₃)₂}₂

Utility of Lithium in Rare-Earth Metal Reduction Reactions to Form Nontraditional Ln²⁺ Complexes and Unusual [Li(2.2.2-cryptand)]¹⁺ Cations

New Homoleptic Rare‐Earth Metal Complexes Comprising the Unsymmetrically Substituted Amidinate Ligand [MeC(NEt)(NtBu)]^–

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Controlled synthesis of lanthanide–lithium inverse crown ether complexes

Cited by 9 publications

References 10 publications

Ni(I) and Ni(II) Bis(trimethylsilyl)amides Obtained in Pursuit of the Elusive Structure of Ni{N(SiMe3)2}2

Ni(I) and Ni(II) Bis(trimethylsilyl)amides Obtained in Pursuit of the Elusive Structure of Ni{N(SiMe3)2}2

Utility of Lithium in Rare-Earth Metal Reduction Reactions to Form Nontraditional Ln2+ Complexes and Unusual [Li(2.2.2-cryptand)]1+ Cations

New Homoleptic Rare‐Earth Metal Complexes Comprising the Unsymmetrically Substituted Amidinate Ligand [MeC(NEt)(NtBu)]–

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Ni(I) and Ni(II) Bis(trimethylsilyl)amides Obtained in Pursuit of the Elusive Structure of Ni{N(SiMe₃)₂}₂

Ni(I) and Ni(II) Bis(trimethylsilyl)amides Obtained in Pursuit of the Elusive Structure of Ni{N(SiMe₃)₂}₂

Utility of Lithium in Rare-Earth Metal Reduction Reactions to Form Nontraditional Ln²⁺ Complexes and Unusual [Li(2.2.2-cryptand)]¹⁺ Cations

New Homoleptic Rare‐Earth Metal Complexes Comprising the Unsymmetrically Substituted Amidinate Ligand [MeC(NEt)(NtBu)]^–