Association of Bis(trimethylsilyl)amidolithium and Methyl(trimethylsilanolato)beryllium in the Solid State

Mootz, D.; Zinnius, A.; Böttcher, Bruno

doi:10.1002/anie.196903781

Cited by 103 publications

(31 citation statements)

References 2 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…[67] For 1, its respective 7 Li NMR spectrum also supports this conclusion as only one resonance (δ = 0.88 ppm) is observed. Higher oligomeric forms (trimer, [30,[68][69][70][71][72] tetramer, [73,74] hexamer [75] and polymer [76] ) of Li amides are known; however, they tend to exist only in the absence of donor solvents.…”

Section: Preparation and Solution Structuresmentioning

confidence: 99%

“…On the other hand, 3 is not soluble in C 6 Primarily to gain a greater understanding of these synthetic endeavours, the structural chemistry of the alkali metal amides has maintained a high level of interest, since the first reported solid-state structure of an alkali metal amide {that of trimeric [Li(hmds)] 3 } in 1969. [30,31] Alkali metal diphenylamide complexes have been extensively studied. The solution structure of LiNPh 2 in thf (in the presence/absence of LiBr) has been comprehensively studied by Collum.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Structural Elucidation of tmeda‐Solvated Alkali Metal Diphenylamide Complexes

et al. 2009

View full text Add to dashboard Cite

Lithium, sodium and potassium salts of diphenylamine have been prepared by using a deprotonative route and characterised in both, solid state (by X‐ray crystallography) and solution (by NMR spectroscopic studies). In each case the metal atom's coordination sphere is completed by coordination to the synthetically important co‐ligand N,N,N′,N′‐tetramethylethylenediamine (tmeda). Complexes 1 and 2 [{(tmeda)M(NPh2)}2] (M = Li for 1, Na for 2) can be prepared by treating 1 mol.‐equiv. of the parent amine with an equimolar quantity of nBuM and tmeda in hexane solution. In the solid state, 1 and 2 are essentially isostructural, being dimeric with a four‐atom M–N–M–N framework. The coordination sphere of each M atom is completed by a bidentate tmeda molecule. Complex 3 [{(tmeda)3/2K(NPh2)}2] has been prepared in a similar way to 1 and 2 except that benzylpotassium has been utilised as the metallating agent. In addition, 4 mol‐equiv. of tmeda is required to fully solubilise the heavy alkali metal amide mixture. In the solid state, 3 exists as a polymeric array of dinuclear K–N–K–N rings. Akin to 1 and 2, the K atom is coordinated to a bidentate tmeda molecule; however, each K atom is also bound to another tmeda molecule that acts as a monodentate bridge, thus producing the coordination polymer. Crystalline 1 and 2 are soluble in C6D6; hence, NMR spectroscopic studies could be performed. These show that the solid‐state structure appears to stay intact in arene solution. On the other hand, 3 is not soluble in C6D6; so solution studies have been performed in [D8]thf. These studies reveal that 3 readily looses tmeda during in‐vacuo isolation. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

show abstract

Section: Preparation and Solution Structuresmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Structural Elucidation of tmeda‐Solvated Alkali Metal Diphenylamide Complexes

et al. 2009

View full text Add to dashboard Cite

show abstract

“…Mit den hier beschriebenen Strukturen von Rb-und CsN(SiMe 3 ) 2 (1 und 2) sind nunmehr die Kristallstrukturen von allen solvatfreien Alkali-hexamethyldisilaziden bekannt (fu È r LiN(SiMe 3 ) 2 siehe [5], fu È r NaN(SiMe 3 ) 2 [6,7] und fu È r KN(SiMe 3 ) 2 [8]). Charakteristisches Bauelement der im Kristall dimeren Rbund Cs-hexamethyldisilazide ist ein vo È llig ebener viergliedriger [M±N±] 2 -Ring (kristallographisches Symmetriezentrum im Ringmittelpunkt).…”

Section: Strukturenunclassified

Kristall- und Molekülstruktur der solvatfreien Hexamethyldisilazide des Rubidiums und Caesiums und die Kristallstruktur eines Toluolsolvates

Neander

Behrens

1999

Z. anorg. allg. Chem.

View full text Add to dashboard Cite

Die Kristallstrukturen der dimeren Rubidium‐ und Caesium‐hexamethyldisilazide [MN(SiMe3)2]2 werden beschrieben. [RbN(SiMe3)2]2 (1) kristallisiert in der monoklinen Raumgruppe P21/c mit a = 1044.7(2), b = 891.1(2), c = 1281.0(3) pm, β = 100.26(2)°, Z = 2. [CsN(SiMe3)2]2 (2) kristallisiert in der orthorhombischen Raumgruppe Pbca mit a = 1270.81(2), b = 1281.16(1), c = 1539.65(2) pm, Z = 4. Beide Verbindungen enthalten einen viergliedrigen [M–N–]2‐Ring, der auf einem Inversionszentrum liegt. Die M–N‐Bindungslängen betragen: 287.8(2), 295.6(2) pm (1) und 307.4(2), 314.9 (2) pm (2). Das Solvat [CsN(SiMe3)2]2 · C7H8 (3) kristallisiert aus Toluol in der triklinen Raumgruppe P1 mit a = 854.00(2), b = 979.58(2), c = 1084.45(3) pm, α = 111.482(1), β = 93.821(1), γ = 108.546(1)°, Z = 1. In dieser Verbindung bilden dimere Einheiten [CsN(SiMe3)2]2 und Toluolmoleküle eine polymere Kette.

show abstract

“…Although these reagents are often used in situ, the solvent-free solid-state structures of the lighter group 1 salts LiN′′ [8,9], NaN′′ [10] and KN′′ [11] have been reported previously. Interestingly, although synthetic routes to alkali metal bis(silyl)amides with larger R groups, {MN(SiR 3 ) 2 } (R = Me, t Bu, i Pr, etc.…”

Section: Introductionmentioning

confidence: 99%

Structural Characterization of Lithium and Sodium Bulky Bis(silyl)amide Complexes

et al. 2018

View full text Add to dashboard Cite

Alkali metal amides are vital reagents in synthetic chemistry and the bis(silyl)amide {N(SiMe3)2} (N′′) is one of the most widely-utilized examples. Given that N′′ has provided landmark complexes, we have investigated synthetic routes to lithium and sodium bis(silyl)amides with increased steric bulk to analyse the effects of R-group substitution on structural features. To perform this study, the bulky bis(silyl)amines {HN(SitBuMe2)(SiMe3)}, {HN(SiiPr3)(SiMe3)}, {HN(SitBuMe2)2}, {HN(SiiPr3)(SitBuMe2)} and {HN(SiiPr3)2} (1) were prepared by literature procedures as colourless oils; on one occasion crystals of 1 were obtained. These were treated separately with nBuLi to afford the respective lithium bis(silyl)amides [Li{μ-N(SitBuMe2)(SiMe3)}]2 (2), [Li{μ-N(SiiPr3)(SiMe3)}]2 (3), [Li{N(SitBuMe2)2}{μ-N(SitBuMe2)2}Li(THF)] (4), [Li{N(SiiPr3)(SitBuMe2)}(DME)] (6) and [Li{N(SiiPr3)2}(THF)] (7) following workup and recrystallization. On one occasion during the synthesis of 4 several crystals of the ‘ate’ complex [Li2{μ-N(SitBuMe2)2}(μ-nBu)]2 (5) formed and a trace amount of [Li{N(SiiPr3)2}(THF)2] (8) was identified during the recrystallization of 7. The reaction of {HN(SitBuMe2)2} with NaH in the presence of 2 mol % of NaOtBu gave crystals of [Na{μ-N(SitBuMe2)2}(THF)]2 (9-THF), whilst [Na{N(SiiPr3)2}(C7H8)] (10) was prepared by deprotonation of 1 with nBuNa. The solid-state structures of 1–10 were determined by single crystal X-ray crystallography, whilst 2–4, 7, 9 and 10 were additionally characterized by NMR and FTIR spectroscopy and elemental microanalysis.

show abstract

Association of Bis(trimethylsilyl)amidolithium and Methyl(trimethylsilanolato)beryllium in the Solid State

Cited by 103 publications

References 2 publications

Structural Elucidation of tmeda‐Solvated Alkali Metal Diphenylamide Complexes

Structural Elucidation of tmeda‐Solvated Alkali Metal Diphenylamide Complexes

Kristall- und Molekülstruktur der solvatfreien Hexamethyldisilazide des Rubidiums und Caesiums und die Kristallstruktur eines Toluolsolvates

Structural Characterization of Lithium and Sodium Bulky Bis(silyl)amide Complexes

Contact Info

Product

Resources

About