Silylhydrazines: Lithium Derivatives Isomerism and Rings

Bode, Katrin; Klingebiel, Uwe

doi:10.1016/s0065-3055(08)60531-6

Cited by 41 publications

(48 citation statements)

References 54 publications

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“…Two main methods for the preparation of these compounds have since been developed [3]: the reaction of halosilanes (Hal: Cl, Br, I) with a) hydrazines and b) lithium hydrazides. Especially lithium derivatives of silyl hydrazines have shown a large variety of substitution and oxidation reactions.…”

Section: Introductionmentioning

confidence: 99%

“…In 1964 Baley and West discovered the migration of silyl groups from one nitrogen atom to the other in silyl hydrazines [4,5]. In the meantime, silyl group migration has been applied to the synthesis of isomeric compounds, as well as to stabilizing elements in lower coordination numbers [3,6,7]. During the last years we studied migrations of hydrogen atoms and silyl groups in the chemistry of silazanes [8] and silyl hydrazines [6,9] both experimentally and by quantum-chemical calculations [10].…”

Section: Introductionmentioning

confidence: 99%

“…During the last years we studied migrations of hydrogen atoms and silyl groups in the chemistry of silazanes [8] and silyl hydrazines [6,9] both experimentally and by quantum-chemical calculations [10]. It was found that in such isomerization reactions hydrogen atoms can migrate from a carbon to a nitrogen atom [3,6] and from one nitrogen to another atom [6].…”

Section: Introductionmentioning

confidence: 99%

“…In spite of the successful use of lithium hydrazides in chemistry, the first crystal structure determinations of these reagents were published as late as in the 1990's [3,6,12]. The crystal structures of solely silylsubstituted hydrazides often show unexpected features.…”

Section: Introductionmentioning

confidence: 99%

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Acyclic and Cyclic Silylaminohydrazines

Klingebiel

Matthes²,

Ringe³

et al. 2009

Zeitschrift Für Naturforschung B

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The reaction of H2N-NH2 with ClSiMe2N(SiMe3)2 in a molar ratio 1 : 2 gave the bis(silylamino) hydrazine [HNSiMe2-N(SiMe3)2]2 (1). Compound 1 forms a monomeric dilithium salt with BuLi. From n-hexane (Me3Si-NSiMe2-NLiSiMe3)2 (2) crystallizes while from THF [Me3Si-NSiMe2- NLi(THF)SiMe3]2 (3) precipitates. Compounds 2 and 3 are formed from 1 via a silyl group migration. In the rearranged salts, the silyl groups are bonded at the hydrazino nitrogen atoms. Hydrolysis of 2 led to the formation of (Me3Si-N-SiMe2-NHSiMe3)2 (4) which is a structural isomer of 1. Ring closure occurs in reactions of 2 or 3 with F3B ・ OEt2 or SiF4. The seven-membered rings (Me3Si- N-SiMe2-NSiMe3)2BF (5) and (Me3Si-NSiMe2-NSiMe3)2SiF2, (6) were isolated as the products. The crystal structures of 2, 3 and 5 have been determined.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Acyclic and Cyclic Silylaminohydrazines

Klingebiel

Matthes²,

Ringe³

et al. 2009

Zeitschrift Für Naturforschung B

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“…Klassische Synthesen von Silylhydrazinen verlaufen über die intermolekulare Halogenwasserstoff-Abspaltung aus Hydrazin und Halogensilanen oder über Reaktionen von Lithiumhydraziden mit Halogensilanen. [9,10,11] So konnte 4 durch Gasphasenreaktion von SiH 3 I mit Hydrazin hergestellt werden. [8,12] Unter Berücksichtigung von Literaturdaten [14] ergibt sich hieraus die Standardbildungsenthalpie für 3 zu DH …”

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N₂(SiCl₃)₄ – ein Hydrazinderivat als unerwartetes Produkt der Reaktion von N₂ mit SiCl₄

2003

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The Reaction of Diazomethane Derivatives with the Dielement Compounds R2Al–AlR2 and R2Ga–GaR2 [R = CH(SiMe3)2] – Insertion versus Fragmentation

Uhl¹,

Hannemann

1999

Eur. J. Inorg. Chem.

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Tetrakis[bis(trimethylsilyl)methyl]dialane(4) 1 reacted with trimethylsilyldiazomethane and bis(trimethylsilyl)diazomethane at room temperature by the insertion of the terminal nitrogen atoms into its aluminium–aluminium bond. As shown by a crystal structure determination, one of the aluminium atoms of each product enhanced its coordination number to four by the interaction with the central nitrogen atom of the C=N–N group, which results in the formation of a three‐membered AlN2 heterocycle bearing an exocyclic N=C double bond. The reactions of the corresponding gallium compound (2) containing a gallium–gallium single bond needed more drastic conditions. Mixtures of many unknown products were formed, and only on treatment with trimethylsilyldiazomethane two compounds could be isolated after repeated recrystallization in yields below 10%, which were characterized by crystal structure determinations. One was identified as the trimeric dialkylgallium cyanide (8) with a nine‐membered Ga3C3N3 heterocycle, and the other one (9) has a dialkylgallium fragment coordinated by both terminal nitrogen atoms of the chelating ligand NH2–N=C(SiMe3)–NH−. Due to the NMR spectroscopic characterization, 8 seems to be tetrameric in solution with an asymmetric structure containing four different gallium atoms. With this unusual structure, the IR spectrum of tetrameric dimethylgallium cyanide could now completely be interpreted, which was published more than 20 years ago.

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Silylhydrazines: Lithium Derivatives Isomerism and Rings

Cited by 41 publications

References 54 publications

Acyclic and Cyclic Silylaminohydrazines

Acyclic and Cyclic Silylaminohydrazines

N₂(SiCl₃)₄ – ein Hydrazinderivat als unerwartetes Produkt der Reaktion von N₂ mit SiCl₄

The Reaction of Diazomethane Derivatives with the Dielement Compounds R2Al–AlR2 and R2Ga–GaR2 [R = CH(SiMe3)2] – Insertion versus Fragmentation

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Silylhydrazines: Lithium Derivatives Isomerism and Rings

Cited by 41 publications

References 54 publications

Acyclic and Cyclic Silylaminohydrazines

Acyclic and Cyclic Silylaminohydrazines

N2(SiCl3)4 – ein Hydrazinderivat als unerwartetes Produkt der Reaktion von N2 mit SiCl4

The Reaction of Diazomethane Derivatives with the Dielement Compounds R2Al–AlR2 and R2Ga–GaR2 [R = CH(SiMe3)2] – Insertion versus Fragmentation

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N₂(SiCl₃)₄ – ein Hydrazinderivat als unerwartetes Produkt der Reaktion von N₂ mit SiCl₄