The reactivity of dimethylaluminum hydride with the aminoarsines Me2AsNMe2, MeAs(NMe2)2, and As(NMe2)3

Watkins, Charles L.; Krannich, L. K.; Thomas, Charles E.; Srivastava, D. K.

doi:10.1016/s0277-5387(00)83111-3

Cited by 7 publications

(8 citation statements)

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“…Conversion of the AlN-containing intermediates to the respective aminoalane dimers is very slow with only 25% conversion to [Bu i 2 AlNPr n 2 ] 2 and 28% conversion to [Bu i 2 AlNBu n 2 ] 2 after 6 months. Me 2 AsH does not appear as a final product due to its reactivity with Me 2 AsR. , …”

Section: Resultsmentioning

confidence: 97%

“…For the Me 2 AlH/Me 2 AsR systems where R = NMe 2 , NPr n 2 , NBu n 2 , NC 4 H 8 , NC 5 H 10 , and NC 6 H 12 , the respective aminoalane dimers are observed immediately after mixing in the 1 H and 13 C NMR. Several AlN-containing intermediates, analogous to 2Me 2 AlNMe 2 ·Me 2 AlH, Me 2 AlNMe 2 ·Me 2 AlH, and [Me 2 AlNMe 2 ·Me 2 AlH] 2 , which were previously identified for the Me 2 AlH/Me 2 AsNMe 2 reaction system, are present in each case. These serve as precursors to the aminoalane dimers.…”

Section: Resultsmentioning

confidence: 99%

“…Recently, we reported an NMR study of the reactivity of Me 2 AlH , toward Me 2 AsNMe 2 and found that the RT (room temperature) 1:1 mol ratio reaction is very exothermic. The 1 H and 13 C NMR spectra indicate that >90% of the reactants are consumed upon mixing with no spectral evidence for an Al−N or Al−As adduct.…”

Section: Introductionmentioning

confidence: 99%

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Reactivity of R₂AlH (R = Me, Buⁱ) with Selected Aminoarsines and Secondary Amines

et al. 1996

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Me2AlH and Bui 2AlH were reacted with a series of nine aminoarsines, Me2AsR (R = NMe2, NPrn 2, NPri 2, NBun 2, NBui 2, NC4H8, NC5H10, NC6H12, and N(C2H4)2NMe), in C6D6 at room temperature, and the reactions were monitored by 1H and 13C NMR spectroscopy. The relative rates for initial As−N bond cleavage and final product formation were dependent on the steric requirements of the alkyl groups attached to aluminum and nitrogen in the starting materials. Overall rates were slower with Bui 2AlH than with Me2AlH for a given aminoarsine. For most of the reactions, the predominant Al-containing products were the dimeric aminoalane compounds, [Me2AlR]2 and [Bui 2AlR]2. Although Al−N bond formation was the prefered mode of reaction, Al−As bond formation was also observed when the bulky Pri and Bui aminoarsine derivatives were used. The [Bui 2AlR]2 compounds were synthesized independently by the reaction of Bui 2AlH and the respective amine or, in the case of [Bui 2AlNBui 2]2, by the reaction of Bui 2AlCl and LiNBui 2. X-ray crystal structures were determined for the compounds [Me2AlNC6H12]2, [Me2AlN(C2H4)2NMe]2, [Bui 2AlNMe2]2, and [Bui 2AlN(C2H4)2NMe]2. All of the compounds have planar Al2N2 rings with the exception of [Bui 2AlN(C2H4)2NMe]2, which displays a puckered Al2N2 ring.

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Section: Resultsmentioning

confidence: 97%

Section: Resultsmentioning

confidence: 99%

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Reactivity of R₂AlH (R = Me, Buⁱ) with Selected Aminoarsines and Secondary Amines

et al. 1996

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“…We postulate that DIBAL-H plays a critical role in activating the arsenic precursor which allows the formation of InAs upon reaction with InCl 3 at elevated temperatures. Alkylaluminum hydrides (such as DIBAL-H) are known to cleave the As–N bond in alkyl substituted aminoarsines to form As–H bonded intermediates and eventually generate As–As bonded species. , For instance, when monoaminodimethylarsine was reacted with dimethylaluminum hydride, dimethylarsine could be isolated as one of the products . Such As–H bonded species are expected to be produced as intermediates when DIBAL-H is reacted with As(NMe 2 ) 3 .…”

Section: Resultsmentioning

confidence: 99%

Facile, Economic and Size-Tunable Synthesis of Metal Arsenide Nanocrystals

et al. 2016

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Synthesis of colloidal nanocrystals (NC) of important arsenide nanomaterials (e.g., InAs, Cd3As2) has been limited by the lack of convenient arsenic precursors. Here we address this constraint by identifying a convenient and commercially available As precursor, tris-dimethylaminoarsine (As(NMe2)3), which can be used to prepare high quality InAs NCs with controlled size distributions. Our approach employs a reaction between InCl3 and As(NMe2)3 using diisobutylaluminum hydride (DIBAL-H) to convert As(NMe2)3 in situ into reactive intermediates AsH x (NMe2)3–x , where x = 1,2,3. NC size can be varied by changing DIBAL-H concentration and growth temperature, with colloidal solutions of InAs showing size dependent absorption and emission features tunable across wavelengths of 750 to 1450 nm. We also show that this approach works well for the colloidal synthesis of Cd3As2 NCs. By circumventing the preparation of notoriously unstable and dangerous arsenic precursors (e.g., AsH3 and As(SiMe3)3), this work improves the synthetic accessibility of arsenide-based NCs and, by extension, the potential of such NCs for use in infrared (IR) applications such as communications, fluorescent labeling and photon detection.

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“…The reaction of As(OLA) 3 with indium(III) chloride (InCl 3 ) to InAs QDs does not proceed without the subsequent addition of a reducing agent for which typically diisobutylaluminum hydride (DIBAL‐ H ) and nowadays also trioleylphosphane (P(OLA) 3 ) or a N,N ‐dimethylethylamine complex (DMEA‐AlH 3 ) are used. In the case of DIBAL‐ H and DMEA‐AlH 3 , the As–N bonds are cleaved to give in situ (OLA) x AsH 3‐ x species which react with the indium precursor to InAs QDs . With the applied concentration of DIBAL‐ H the size of InAs QDs can be tuned according to the method by Srivastava et al By contrast, the approach by Grigel et al applies in situ generated P(OLA) 3 as reducing agent for the InAs QD synthesis ( Scheme ).…”

Section: Introductionmentioning

confidence: 99%

Synthesis of NIR‐Emitting InAs‐Based Core/Shell Quantum Dots with the Use of Tripyrazolylarsane as Arsenic Precursor

Tietze

Panzer

Starzynski

et al. 2018

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arsenic precursor [2,16] besides the less reactive tris(trimethylgermyl)arsane (As(GeMe 3 ) 3 ) [17] or highly toxic arsine gas (AsH 3 ). [18] Recently, Srivastava et al. [19] and Grigel et al. [20] highlighted tris(dimethylamino)arsane (As(NMe 2 ) 3 ) as commercially available pre cursor for the facile synthesis of InAs QDs. Mechanistically, As(NMe 2 ) 3 undergoes a transamination reaction with the solvent and reagent oleylamine (OLAH) to give trioleyl arsane (As(OLA) 3 ) under the release of three equivalents of flammable dimethylamine. The reaction of As(OLA) 3 with indium(III) chloride (InCl 3 ) to InAs QDs does not proceed without the subsequent addition of a reducing agent for which typically diisobutylaluminum hydride (DIBALH) [19] and nowadays also trioleylphosphane (P(OLA) 3 ) [20] or a N,Ndimethylethylamine com plex (DMEAAlH 3 ) [21] are used. In the case of DIBALH and DMEA AlH 3 , the As-N bonds are cleaved to give in situ (OLA) x AsH 3x species which react with the indium precursor to InAs QDs. [22,23] With the applied concentration of DIBALH the size of InAs QDs can be tuned according to the method by Srivastava et al. [19] By contrast, the approach by Grigel et al. [20] applies in situ generated P(OLA) 3 as reducing agent for the InAs QD synthesis (Scheme 1). This species is known to act both, as a remarkably efficient phos phorus precursor and reducing agent for the preparation of InP QDs. [24][25][26] Grigel et al. [20] pointed out that phase pure InAs QDs are obtained since P(OLA) 3 only provides the electrons required for the reduction of As(OLA) 3 to InAs (Scheme 1).In previous work we introduced tripyrazolylphosphanes (P(pyr) 3 , e.g., pyr = 3,5dimethylpyrazole, 2) for the convenient preparation of a long term stable (>6 months) P(OLA) 3 stock solution and its application for the synthesis of highly emitting InP/ZnS QDs. [5,6] Derivatives of P(pyr) 3 are accessible on a multigram scale and represent a safe to handle, less toxic sur rogate for cancerogenic hexaalkylphosphorous triamide deriva tives such as trisdimethylaminophosphane (P(NMe 2 ) 3 ) and tris diethylaminophosphane (P(NEt 2 ) 3 ). Moreover, the release of cor rosive, flammable, and gaseous dialkylamines (Me 2 NH, Et 2 NH) during the transamination with OLAH is prevented. The released pyrazoles can easily be recovered in high yields (>94%) and reused for the precursor synthesis. The tripyrazolylarsane (As(pyr) 3 , e.g., pyr = 3,5dimethylpyrazole, 1) analogues are envisioned to react similarly, thus, representing a convenient to handle and stable arsenic precursor for the InAs QD synthesis. Tris(3,5-dimethylpyrazolyl)arsane (1) is introduced as a low-cost and convenient to handle arsenic precursor for the straight forward synthesis of InAs quantum dots (QDs). Transamination of 1 with the solvent oleylamine (OLAH) gives trioleylarsane (As(OLA) 3 ) which in the presence of the reducing agents diisobutylaluminum hydride (DIBAL-H) or trioleylphosphane (P(OLA) 3 ) yields InAsQDs via a typical hot injection approach. The size of the obtain...

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The reactivity of dimethylaluminum hydride with the aminoarsines Me2AsNMe2, MeAs(NMe2)2, and As(NMe2)3

Cited by 7 publications

References 23 publications

Reactivity of R₂AlH (R = Me, Buⁱ) with Selected Aminoarsines and Secondary Amines

Reactivity of R₂AlH (R = Me, Buⁱ) with Selected Aminoarsines and Secondary Amines

Facile, Economic and Size-Tunable Synthesis of Metal Arsenide Nanocrystals

Synthesis of NIR‐Emitting InAs‐Based Core/Shell Quantum Dots with the Use of Tripyrazolylarsane as Arsenic Precursor

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The reactivity of dimethylaluminum hydride with the aminoarsines Me2AsNMe2, MeAs(NMe2)2, and As(NMe2)3

Cited by 7 publications

References 23 publications

Reactivity of R2AlH (R = Me, Bui) with Selected Aminoarsines and Secondary Amines

Reactivity of R2AlH (R = Me, Bui) with Selected Aminoarsines and Secondary Amines

Facile, Economic and Size-Tunable Synthesis of Metal Arsenide Nanocrystals

Synthesis of NIR‐Emitting InAs‐Based Core/Shell Quantum Dots with the Use of Tripyrazolylarsane as Arsenic Precursor

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Reactivity of R₂AlH (R = Me, Buⁱ) with Selected Aminoarsines and Secondary Amines

Reactivity of R₂AlH (R = Me, Buⁱ) with Selected Aminoarsines and Secondary Amines