A tetranuclear aluminium hydrazide derivative with a ladder-type structure

Silverman, Joel S.; Abernethy, Colin D.; Jones, Richard A.; Cowley, Alan H.

doi:10.1039/a904046c

Cited by 35 publications

(53 citation statements)

References 16 publications

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“…We have firmly established, through structural and spectroscopic studies, a new class of organometallic compounds of zinc with novel Zn 4 (22A) 1.447(6) N(22A)ÀZn (3A) 2.005 (5) Scheme 4. Further investigations into new substitution patterns, involvement of other OH-functional compounds in the alcoholysis or one-pot reactions and new aggregation modes are in progress as well as thermal decomposition experiments of these cluster compounds under different conditions.…”

Section: Resultsmentioning

confidence: 99%

“…The clear, colourless filtrate, when stored at À10 8C, afforded colourless crystals of 1 and 2. 4 (OH)(NHNMe 2 ) 3 ] (4) synthesis: E 2 Zn (E = Me, Et) (5 mL, 2 m, in n-hexane/toluene; 10 mmol) was added dropwise via a syringe to a stirred solution of H 2 NNMe 2 (0.6 mL, 7.83 mmol) in n-hexane (10 mL) at 0 8C. Water (0.07 mL, 3.88 mmol) was added dropwise via a syringe.…”

Section: Methodsmentioning

confidence: 97%

“…They contain Zn 4 N 6 O cages, in which one hydroxide in the tetrameric hydrazides described above replaces one NHNMe 2 group. Similar products can be prepared with alkoxy instead of hydroxy groups, in analogous one-pot syntheses with alco- 4 (NHNMe 2 ) 2 (OEt) 2 ] were obtained in one-pot reactions from dialkylzinc solutions with mixtures of the hydrazine and alcohol, and their crystal structures, confirmed by spectroscopic methods in solution, show an unsymmetrical aggregation with the novel Zn 4 N 4 O 2 cage structure.…”

Section: Introductionmentioning

confidence: 91%

“…[4] The wealth of different aggregation modes in such metal hydrazides originates from the presence of two directly connected donor sites. A, B and C are examples of typical bridging modes that have been found in various metal hydrazides.…”

Section: Introductionmentioning

confidence: 99%

“…The NH groups are connected to two Zn atoms, and the NMe 2 groups to one. Hydrolysis of the compounds with water gives [(RZn) 4 (OH)(NHNMe 2 ) 3 ] as products, which also were characterised as described above. Higher yields of these hydroxo clusters were achieved in onepot syntheses by reaction of dialkylzinc solutions with mixtures of N,N-dimethylhydrazine and water.…”

Section: Introductionmentioning

confidence: 99%

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Zinc Hydrazides and Alkoxyhydrazides: Organometallic Compounds with Novel Zn₄N₈, Zn₄N₆O and Zn₄N₄O₂ Cage Structures

Jana

Fröhlich

Mitzel

2005

Chemistry A European J

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Tetrameric [{RZn(NHNMe2)}4] (R = Me, Et), the first organometallic zinc hydrazides to be described, have been prepared by alkane elimination from dialkylzinc solutions and N,N-dimethylhydrazine. They were characterised by 1H and 13C NMR and IR spectroscopy, mass spectrometry, elemental analysis and X-ray crystallography. The compounds form asymmetric aggregates containing the novel Zn4N8 core; tetrahedra of Zn atoms bear the alkyl groups at Zn, with the triangular faces bridged by NHNMe2 substituents. The NH groups are connected to two Zn atoms, and the NMe2 groups to one. Hydrolysis of the compounds with water gives [(RZn)4(OH)(NHNMe2)3] as products, which also were characterised as described above. Higher yields of these hydroxo clusters were achieved in one-pot syntheses by reaction of dialkylzinc solutions with mixtures of N,N-dimethylhydrazine and water. They contain Zn4N6O cages, in which one hydroxide in the tetrameric hydrazides described above replaces one NHNMe2 group. Similar products can be prepared with alkoxy instead of hydroxy groups, in analogous one-pot syntheses with alcohols. Alcoholysis of [EtZn(NHNMe2)]4 with methanol or ethanol gave zinc trishydrazide monoalkoxides, [(EtZn)4(OR)(NHNMe2)3] (R = Me, Et), which have constitutions analogous to the monohydroxides. The organozinc bishydrazide bisalkoxides [(MeZn)4(NHNMe2)2(OEt)2] and [(EtZn)4(NHNMe2)2(OEt)2] were obtained in one-pot reactions from dialkylzinc solutions with mixtures of the hydrazine and alcohol, and their crystal structures, confirmed by spectroscopic methods in solution, show an unsymmetrical aggregation with the novel Zn4N4O2 cage structure.

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Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 97%

Section: Introductionmentioning

confidence: 91%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Zinc Hydrazides and Alkoxyhydrazides: Organometallic Compounds with Novel Zn₄N₈, Zn₄N₆O and Zn₄N₄O₂ Cage Structures

Jana

Fröhlich

Mitzel

2005

Chemistry A European J

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Aluminium Hydrazides: Dimeric Bis(tert-butyl)aluminium Hydrazides withSix-Membered Al2N4 and Five-Membered Al2N3 Heterocycles

Uhl

Molter

Koch

2000

Eur. J. Inorg. Chem.

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Treatment of the hydrazine adduct (Me3C)2AlCl·NH2NHSiMe3 (2) with n‐butyllithium afforded the colorless dialkylaluminium hydrazide (Me3C)2AlN(SiMe3)NH2 (3) by the release of butane and the precipitation of LiCl. Hydrazide 3 gave a dimer in solution and in the solid state. As shown by a crystal structure determination, a six‐membered Al2N4 heterocycle with two intact endocyclic N−N bonds was formed by a head‐to‐tail dimerization. Upon sublimation of 3 in vacuum, a rearrangement was observed which gave an isomeric compound 4 after the migration of a hydrogen atom of a hydrazido ligand. The molecular core of 4 comprises a five‐membered Al2N3 heterocycle, in which the Al atoms are bridged by one hydrazido ligand similar to 3. The second ligand, however, has only one nitrogen atom in a bridging position with an exocyclic N−N bond. A similar compound (5) was obtained by the reaction of bis(tert‐butyl)aluminium chloride with phenylhydrazine and n‐butyllithium.

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Hydrazino Derivatives of Gallanes and Indanes − Synthesis and Structures

Nöth

Seifert

2002

Eur. J. Inorg. Chem.

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The reaction of Me2GaCl with tBuHN−NH2 proceeds with ligand exchange at the gallium atom leading to MeCl2Ga·H2N−NHtBu (1). On the other hand, only one methyl group of the trimethylgallium molecule reacts in refluxing toluene with anhydrous hydrazine in a 4:3 ratio to produce the bicyclic dimethylgallium hydrazide 3. N‐Lithio‐N‐trimethylsilyl‐N′‐2‐naphthylhydrazine reacts with dimethylgallium chloride, not only by introducing a gallium atom into the hydrazine unit, but also by inducing CH activation at the 1‐position of the naphthyl group with methane evolution. The main product isolated is the 2,3‐dihydro‐1H‐naphtho[1,2‐d][1,2,3]diazagallol 4 which proved to be dimeric. A 1:1 GaMe3 adduct of Li(Me3Si)N−NHtBu (5) is the unexpected compound in the reaction of Me2GaCl with Li(Me3Si)N−NHtBu. The expected substitution product Me2Ga(Me3Si)N−NHtBu is not formed. Compound 5 is a dimer in the solid state. The products obtained from reactions of Li(Me3Si)N−NHtBu with Me2InCl depend on the solvent. With hexane as a solvent the dimeric trimethylindium adduct of Li(Me3Si)N−NHtBu (7), is produced as the main species. In diethyl ether the cage compound 8 is isolated which can be regarded as an (Me3SiN=InMe)2 adduct with [Li(Me3Si)N−NHtBu]2. Moreover, the reaction of Me2InCl in diethyl ether with the bulky lithium hydrazide Li[Me3SiN−N(SiMe3)2] leads not to the substitution product, but to the dimeric adduct 9 of a diindoxane, Me2In−O−InMe2 with Li(Me3Si)N−N(SiMe3)2. The formation of this product indicates that ether cleavage or hydrolysis (during crystallization) has occurred.

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A tetranuclear aluminium hydrazide derivative with a ladder-type structure

Abstract: The reaction of (Me 2 NAlH 2 ) 3 with excess H 2 NNMe 2 affords [Al 4 (NHNMe 2 ) 6 (NNMe 2 ) 4 ]; the compound possesses an Al 4 N 4 ladder-shaped core.

Cited by 35 publications

References 16 publications

Zinc Hydrazides and Alkoxyhydrazides: Organometallic Compounds with Novel Zn₄N₈, Zn₄N₆O and Zn₄N₄O₂ Cage Structures

Zinc Hydrazides and Alkoxyhydrazides: Organometallic Compounds with Novel Zn₄N₈, Zn₄N₆O and Zn₄N₄O₂ Cage Structures

Aluminium Hydrazides: Dimeric Bis(tert-butyl)aluminium Hydrazides withSix-Membered Al2N4 and Five-Membered Al2N3 Heterocycles

Hydrazino Derivatives of Gallanes and Indanes − Synthesis and Structures

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A tetranuclear aluminium hydrazide derivative with a ladder-type structure

Abstract: The reaction of (Me 2 NAlH 2 ) 3 with excess H 2 NNMe 2 affords [Al 4 (NHNMe 2 ) 6 (NNMe 2 ) 4 ]; the compound possesses an Al 4 N 4 ladder-shaped core.

Cited by 35 publications

References 16 publications

Zinc Hydrazides and Alkoxyhydrazides: Organometallic Compounds with Novel Zn4N8, Zn4N6O and Zn4N4O2 Cage Structures

Zinc Hydrazides and Alkoxyhydrazides: Organometallic Compounds with Novel Zn4N8, Zn4N6O and Zn4N4O2 Cage Structures

Aluminium Hydrazides: Dimeric Bis(tert-butyl)aluminium Hydrazides withSix-Membered Al2N4 and Five-Membered Al2N3 Heterocycles

Hydrazino Derivatives of Gallanes and Indanes − Synthesis and Structures

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Zinc Hydrazides and Alkoxyhydrazides: Organometallic Compounds with Novel Zn₄N₈, Zn₄N₆O and Zn₄N₄O₂ Cage Structures

Zinc Hydrazides and Alkoxyhydrazides: Organometallic Compounds with Novel Zn₄N₈, Zn₄N₆O and Zn₄N₄O₂ Cage Structures