Structure of potassium hexamethyldisilazide toluene solvate

Williard, P. G.

doi:10.1107/s0108270187008497

Cited by 26 publications

(26 citation statements)

References 2 publications

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“…The formation of M 2 N 2 ring dimers was anticipated as this is the most commonly found aggregation state for monoA C H T U N G T R E N N U N G denA C H T U N G T R E N N U N G tate solvates of the alkali metal hexamethyldisilazides (Table 2). [66][67][68][69][70][72][73][74][75] As expected, the metrical parameters within the dimeric units for each compound are very similar to those of the comparable solvates. The M À N and the Si À N distances in 1-4 all lie within the range of bond lengths found for the previously characterized dimeric complexes.…”

Section: Resultssupporting

confidence: 50%

“…The most closely related arene-solvated analogues of 1-4 are the toluene complexes [(Me 3 Si) 2 NK·A C H T U N G T R E N N U N G (Tol)] 2 (7) [72] and (8). [75] Complex 7 is a simple molecular dimer, with terminal toluene molecules h 6 -bound to the metal centers.…”

Section: Resultsmentioning

confidence: 99%

“…[63] We selected the alkali metal hexamethyldisilazides (M-A C H T U N G T R E N N U N G (HMDS); M = Li, Na, K, Rb, Cs) for study as they combine several attractive features: 1) they are all known to form dimeric M 2 N 2 ring structures upon solvation with appropriate Lewis bases, [64][65][66][67][68][69][70][71][72][73][74][75] 2) they are soluble in arene media without the need for the addition of donor solvents, and 3) both KHMDS and CsHMDS crystallize as bis(h 6 -toluene)-solvated dimers, demonstrating their ability to support cation-p interactions. [72,75] Overall, it was envisioned that ferrocene would act as a ditopic linker to create one-dimensional chains of dimers in each case.…”

Section: ·A C H T U N G T R E N N U N G (Tol) 2 ] + [Mga C H T U N G mentioning

confidence: 99%

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Organometallic Polymers Assembled from Cation–π Interactions: Use of Ferrocene as a Ditopic Linker Within the Homologous Series [{(Me₃Si)₂NM}₂⋅(Cp₂Fe)]_∞ (M=Na, K, Rb, Cs; Cp=cyclopentadienyl)

Morris

Noll

Honeyman

et al. 2007

Chemistry A European J

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Addition of ferrocene to solutions of alkali metal hexamethyldisilazides M(HMDS) in arenes (in which M=Na, K, Rb, Cs) allows the subsequent crystallization of the homologous series of compounds [{(Me(3)Si)(2)NM}(2) (Cp(2)Fe)](infinity) (1-4). Similar reactions using LiHMDS led to the recrystallization of the starting materials. The crystal structures of 1-4 reveal the formation of one-dimensional chains composed of dimeric [{M(HMDS)}(2)] aggregates, which are bridged through neutral ferrocene molecules by eta(5)-cation-pi interactions. In addition, compounds 3 and 4 also contain interchain agostic M--C interactions, producing two-dimensional 4(4)-nets. Whereas 1 and 2 were prepared from toluene, the syntheses of 3 and 4 required the use of tert-butylbenzene as the reaction media. The attempted crystallization of 3 and 4 from toluene resulted in formation of the mixed toluene/ferrocene solvated complexes [{(Me(3)Si)(2)NM)(2)}(2) (Cp(2)Fe)(x)(Tol)(y)](infinity) (in which M=Rb, x=0.6, y=0.8, 5; M=Cs, x=0.5, y=1, 6). The extended solid-state structures of 5 and 6 are closely related to the 4(4)-sheets 3 and 4, but are now assembled from a combination of cation-pi, agostic, and pi-pi interactions. The charge-separated complex [K{(C(6)H(6))(2)Cr}(1.5)(Mes)][Mg(HMDS)(3)] (15) was also structurally characterized and found to adopt an anionic two-dimensional 6(3)-network through doubly eta(3)-coordinated bis(benzene)chromium molecules. DFT calculations at the B3 LYP/6-31G* level of theory indicate that the binding energies of both ferrocene and toluene to the M(HMDS) dimers increases in the sequence Li

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Section: Resultssupporting

confidence: 50%

Section: Resultsmentioning

confidence: 99%

Section: ·A C H T U N G T R E N N U N G (Tol) 2 ] + [Mga C H T U N G mentioning

confidence: 99%

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Organometallic Polymers Assembled from Cation–π Interactions: Use of Ferrocene as a Ditopic Linker Within the Homologous Series [{(Me₃Si)₂NM}₂⋅(Cp₂Fe)]_∞ (M=Na, K, Rb, Cs; Cp=cyclopentadienyl)

Morris

Noll

Honeyman

et al. 2007

Chemistry A European J

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“…Die Differenzen bei den entsprechenden M±N-Absta È nden betragen 13 und 33 pm. Subtrahiert man die Ionenradien der Alkaliionen (Li: 76 pm, Na: 102 pm, jeweils CN = 6 [19] (1) 188.8 (3) Si (1)±C (2) 188.3(3) Si(1)±C (3) 189.8 (3) Si (2)±C (4) 187.6(3) Si (2)±C (5) 190.6 (3) Si (2) [9] werden hingegen K±C-Absta È nde zwischen 318.8 und 335.7 pm gefunden [9]. Hier unterschreiten einige K±C-Wechselwirkungen die Summe der van-derWaals-Radien (323 pm).…”

Section: Strukturenunclassified

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

Neander

Behrens

1999

Z. anorg. allg. Chem.

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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.

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“…The phenyl groups in A are orthogonal to those in B. A list of selected interatomic bond lengths (Å ) and angles (°) together with those of a related compound [K{µ-N(SiMe 3 ) 2 }] 2 [23] are in [23,24] only the Si(1)ϪNϪSi(2) and SiB(1)ϪNBϪSiB (2) 23] ] angles show significant differences. As shown by a portion of the structure of 4 depicted in Figure 3, close contacts between a potassium atom (say in B) and the phenyl ring of the neighbouring unit (say A) are present: [KϪC(2) 3.512(2), KϪC(3) 3.119(2), KϪC(4) [23] and also, as a referee (but not refs.…”

Section: Angles Bondmentioning

confidence: 99%

Synthesis and Structures of Alkali Metal Amides Derived from the Ligands [N(SiMe₂Ph)(SiMe₃)]⁻, [N(tBu)(SiMe₃)]⁻, [N(Ph)(2‐C₅H₄N)]⁻, and [N(2‐C₅H₄N)₂]⁻

et al. 2003

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The following crystalline complexes are reported: [(M{μ‐N(SiMe2Ph)(SiMe3)})2]n [the cis complex for n = 1 and M = Li (1); and the trans complexes with n = ∞ and M = Na (2), K (4), Rb (5), Cs (6)], [(Na{μ‐trans‐N(SiMe2Ph)(SiMe3)})2(tmeda)] (3), [(K{μ‐trans‐N(tBu)(SiMe3)})4(η‐C6H6)2] (7), [(K{μ‐trans‐N(Ph)(2‐C5H4N)})2(μ′‐thf)3]∞ (8), and [K{μ‐N(2‐C5H4N)2}]∞ (9). Each, except 3, was obtained by metallation of the appropriate secondary amine with LinBu (for 1), MBzl [M = Na (for 2), K (for 4 and 7), Rb (for 5), Cs (for 6)], or KH (for 8 and 9); treatment of 2 with an excess of tmeda yielded 3. Each of 1−9 has an unusual, and in some cases unprecedented, molecular structure. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)

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Structure of potassium hexamethyldisilazide toluene solvate

Cited by 26 publications

References 2 publications

Organometallic Polymers Assembled from Cation–π Interactions: Use of Ferrocene as a Ditopic Linker Within the Homologous Series [{(Me₃Si)₂NM}₂⋅(Cp₂Fe)]_∞ (M=Na, K, Rb, Cs; Cp=cyclopentadienyl)

Organometallic Polymers Assembled from Cation–π Interactions: Use of Ferrocene as a Ditopic Linker Within the Homologous Series [{(Me₃Si)₂NM}₂⋅(Cp₂Fe)]_∞ (M=Na, K, Rb, Cs; Cp=cyclopentadienyl)

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

Synthesis and Structures of Alkali Metal Amides Derived from the Ligands [N(SiMe₂Ph)(SiMe₃)]⁻, [N(tBu)(SiMe₃)]⁻, [N(Ph)(2‐C₅H₄N)]⁻, and [N(2‐C₅H₄N)₂]⁻

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Structure of potassium hexamethyldisilazide toluene solvate

Cited by 26 publications

References 2 publications

Organometallic Polymers Assembled from Cation–π Interactions: Use of Ferrocene as a Ditopic Linker Within the Homologous Series [{(Me3Si)2NM}2⋅(Cp2Fe)]∞ (M=Na, K, Rb, Cs; Cp=cyclopentadienyl)

Organometallic Polymers Assembled from Cation–π Interactions: Use of Ferrocene as a Ditopic Linker Within the Homologous Series [{(Me3Si)2NM}2⋅(Cp2Fe)]∞ (M=Na, K, Rb, Cs; Cp=cyclopentadienyl)

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

Synthesis and Structures of Alkali Metal Amides Derived from the Ligands [N(SiMe2Ph)(SiMe3)]−, [N(tBu)(SiMe3)]−, [N(Ph)(2‐C5H4N)]−, and [N(2‐C5H4N)2]−

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Organometallic Polymers Assembled from Cation–π Interactions: Use of Ferrocene as a Ditopic Linker Within the Homologous Series [{(Me₃Si)₂NM}₂⋅(Cp₂Fe)]_∞ (M=Na, K, Rb, Cs; Cp=cyclopentadienyl)

Organometallic Polymers Assembled from Cation–π Interactions: Use of Ferrocene as a Ditopic Linker Within the Homologous Series [{(Me₃Si)₂NM}₂⋅(Cp₂Fe)]_∞ (M=Na, K, Rb, Cs; Cp=cyclopentadienyl)

Synthesis and Structures of Alkali Metal Amides Derived from the Ligands [N(SiMe₂Ph)(SiMe₃)]⁻, [N(tBu)(SiMe₃)]⁻, [N(Ph)(2‐C₅H₄N)]⁻, and [N(2‐C₅H₄N)₂]⁻