Reactions of β-diketiminatoaluminum hydrides with tert-butyl hydrogenperoxide – Facile formation of dialuminoxanes containing Al–O–Al groups

Uhl, Werner; Jana, Barun

doi:10.1016/j.jorganchem.2008.09.036

Cited by 26 publications

(14 citation statements)

References 37 publications

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“…The molecule lies on a special position, with a crystallographically imposed symmetry plane running through atoms C(7), Al(1), C(1), and C(4). The Al(1) center is attached to the C(1) atom of the Cp* ligand with a distance of 2.0901(19) Å, which is 0.109 Å longer than the average Al–C distance in four-coordinate hydrido alkyl aluminum compounds (1.981 Å) . Such an elongated Al–C bond and the acute C(2)–C(1)–Al(1) bond angle of 97.07(10)° indicate that bonding of Al(1) to the Cp* ring has a significant p-character on carbon, which is consistent with the facile haptotropic shift of the Cp* ligand observed by 1 H NMR.…”

Section: Resultsmentioning

confidence: 99%

Oxidative Addition of σ Bonds to an Al(I) Center

2014

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The Al(I) compound NacNacAl (1, NacNac = [ArNC(Me)CHC(Me)NAr](-) and Ar = 2,6-Pr(i)2C6H3) reacts with H-X (X = H, Si, B, Al, C, N, P, O) σ bonds of H2, silanes, borane (HBpin, pin = pinacolate), allane (NacNacAlH2), phosphine (HPPh2), amines, alcohol (Pr(i)OH), and Cp*H (Cp* = pentamethylcyclopentadiene) to give a series of hydride derivatives of the four-coordinate aluminum NacNacAlH(X), which are characterized herein by spectroscopic methods (NMR and IR) and X-ray diffraction. This method allows for the syntheses of the first boryl hydride of aluminum and novel silyl hydride and phosphido hydride derivatives. In the case of the addition of NacNacAlH2, the reaction is reversible, proving the possibility of reductive elimination from the species NacNacAlH(X).

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Section: Resultsmentioning

confidence: 99%

Oxidative Addition of σ Bonds to an Al(I) Center

2014

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“…Similarly, the reaction of Nacnac aluminum hydrides with a variety of OH-containing substrates (e.g., alcohols, silanols, phosphorus(V) acids, peroxides) has been explored by multiple research groups, affording the dehydroalumination products 492 – 497 (Scheme ). − Even less acidic substrates (e.g., amines) are amenable to this dehydrocoupling reaction, as DippNH 2 was shown to react with ( Dipp Nacnac)AlH 2 ( 485 ) to afford the mono-substituted amido-aluminum hydride [( Dipp Nacnac)AlH(NHDipp)] ( 499 ) . Interestingly, when the amine-boranes DippNH 2 ·BH 3 or t BuNH 2 ·BH 3 are used, amine elimination is observed and the κ 2 -borohydride complexes 500 and 501 can be isolated (Scheme ).…”

Section: Molecular Hydrides Of Group 13 Metals (Aluminum Gallium Indi...mentioning

confidence: 99%

Molecular Main Group Metal Hydrides

et al. 2021

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This review serves to document advances in the synthesis, versatile bonding, and reactivity of molecular main group metal hydrides within Groups 1, 2, and 12−16. Particular attention will be given to the emerging use of said hydrides in the rapidly expanding field of Main Group element-mediated catalysis. While this review is comprehensive in nature, focus will be given to research appearing in the open literature since 2001.

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“…The extraordinary protection of the metal center with a β-diketiminato ligand is well-known especially for the stabilization of organometallic compounds of low valent and low coordinate metal centers . Supported by such a ligand, reactions of oxygen-containing compounds with organoaluminum dihydrides − or dihalides , provided facile access to the formation of dialuminoxanes. However, the reactions involving methylaluminum monochlorides resulted in different products.…”

Section: Introductionmentioning

confidence: 99%

Studies of the Ligand Effect on the Synthesis of Dialuminoxanes by Various β-Diketiminato Ligands

Yang

Wang

et al. 2012

Inorg. Chem.

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Reactions of LH (L = HC[C(Me)N(2,6-Me(2)C(6)H(3))](2)) with Me(n)AlCl(3-n) in diethyl ether afforded the adducts LH·AlMe(n)(Cl)(3-n) (n = 2, 3; 1, 4; 0, 5) in good yields. Treatment of 3 at elevated temperatures in toluene resulted in LAlMeCl (2) by intramolecular elimination of methane. The controlled hydrolysis of LAlMeCl (2) with equimolar amounts of water in the presence of N-heterocyclic carbene (NHC) gave a mixture of [LAl(Me)](2)(μ-O) (7) and dimeric [LAlMe(μ-OH)](2) (8). A convenient route for the preparation of [LAlMe(μ-OH)](2) (8) was the NHC-assisted controlled hydrolysis of LAlMeI (9). Stepwise hydrolysis of LAlH(2) (11) gave dialuminoxane hydride [LAl(H)](2)(μ-O) (12) and dialuminoxane hydroxide [LAl(OH)](2)(μ-O) (13), respectively. Anhydrous treatment of LAlCl(2) (1) or LAlMeCl (2) with Ag(2)O afforded chlorinated dialuminoxane [LAl(Cl)](2)(μ-O) (14) and [LAl(Me)](2)(μ-O) (7), respectively.

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Reactions of β-diketiminatoaluminum hydrides with tert-butyl hydrogenperoxide – Facile formation of dialuminoxanes containing Al–O–Al groups

Cited by 26 publications

References 37 publications

Oxidative Addition of σ Bonds to an Al(I) Center

Oxidative Addition of σ Bonds to an Al(I) Center

Molecular Main Group Metal Hydrides

Studies of the Ligand Effect on the Synthesis of Dialuminoxanes by Various β-Diketiminato Ligands

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