Aminoalane Dimers and Trimers. An Examination of Structural and Steric Trends

Schauer, Steven J.; Robinson, Gregory H.

doi:10.1080/00958979308022752

Cited by 33 publications

(21 citation statements)

References 37 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Compounds 1, 2 and 3 have been characterized by 1 H, 13 C and 27 Al NMR spectroscopy as well as by elemental analysis. Single crystal X-ray analysis indicates that the two adducts exist as ten-membered heterocycles with tetracoordinated aluminium centers.Owing to their fundamentally appealing structural diversity [1][2][3] and their use as AlN single source precursors, 4 aluminium amides have been the subjects of numerous investigations. For the most part, previous achievements have been concerned with aluminium derivatives of monofunctional amines.…”

mentioning

confidence: 99%

See 1 more Smart Citation

Reaction of N,N′-bis(mesityl)ethylenediamine with triethylaluminium. Formation of ten-membered aluminium amide heterocycles

2001

New J. Chem.

View full text Add to dashboard Cite

Reaction of N,N 0 -bis(mesityl)ethylenediamine with triethylaluminium in benzene leads to the formation of an aluminium diamide derivative of formula [AlEt(m-MesNCH 2 CH 2 NMes)] n (1) (Mes ¼ 2,4,6-Me 3 C 6 H 2 ). Upon treatment with pyridine or THF, compound 1 is converted into dinuclear aluminium amide derivatives of general formula [AlEt(m-MesNCH 2 CH 2 NMes)] 2 Á 2L with L ¼ pyridine (2) and THF (3), respectively. Compounds 1, 2 and 3 have been characterized by 1 H, 13 C and 27 Al NMR spectroscopy as well as by elemental analysis. Single crystal X-ray analysis indicates that the two adducts exist as ten-membered heterocycles with tetracoordinated aluminium centers.Owing to their fundamentally appealing structural diversity [1][2][3] and their use as AlN single source precursors, 4 aluminium amides have been the subjects of numerous investigations. For the most part, previous achievements have been concerned with aluminium derivatives of monofunctional amines. The chemistry of organoaluminium compounds with chelating bifunctional amido ligands (A) has been less extensively investigated. Despite their rarity, a series of applications identified in the general area of catalysis substantiate the extensively importance of such derivatives. In particular, these compounds have proved useful for the Lewis acid activation of organic reactions 5-8 as well as for the polymerization of olefins. 9 The Lewis acidity and hence, the ability of these compounds 5 to complex incoming nucleophiles, is a crucial parameter that dictates the catalytic properties of such derivatives. Interestingly, while the formation of Lewis adducts has often been proposed, very few studies have focused on the structural characterization of such adducts. In fact, it seems surprising that only one Lewis adduct of these derivatives, namely AlMe{[N(SO 2 CF 3 )-CH( i Pr)CH 2 ] 2 N (CH 2 Ph)} Á DMF, has been isolated and structurally characterized. 8 In this contribution we report on the preparation of one organoaluminium bifunctional amide derivative, [AlEt(m-MesNCH 2 CH 2 NMes)] n (1) and two compounds of general formula [AlEt(m-MesNCH 2 CH 2 NMes)] 2 Á 2L [L ¼ pyridine (2), tetrahydrofuran (3)] that are derived from the reactions between 1 and the appropriate Lewis base. Results and discussionSynthesis and characterization of [AlEt(m-MesNCH 2 -CH 2 NMes)] n (1)The ethylaluminium diamide 1 is obtained in 76% yield by stirring and refluxing a benzene solution containing equimolar amounts of AlEt 3 and the diamine (Scheme 1). Compound 1 is soluble in benzene, toluene, and chloroform, but only slightly soluble in aliphatic solvents and diethyl ether. Scheme 1 A number of spectroscopic features indicate that 1 oligomerizes in solution. First, the 27 Al NMR spectrum of 1 in benzene solution consists of a single resonance at d 63.3 (o 1=2 ¼ 3853 Hz). This resonance clearly differs from that typically observed for tricoordinate aluminium species with two amido ligands 10 and falls at the lower end of the range usually considered for tetracoordinate species....

show abstract

mentioning

confidence: 99%

“…Owing to their fundamentally appealing structural diversity [1][2][3] and their use as AlN single source precursors, 4 aluminium amides have been the subjects of numerous investigations. For the most part, previous achievements have been concerned with aluminium derivatives of monofunctional amines.…”

mentioning

confidence: 99%

Reaction of N,N′-bis(mesityl)ethylenediamine with triethylaluminium. Formation of ten-membered aluminium amide heterocycles

2001

New J. Chem.

View full text Add to dashboard Cite

show abstract

“…2 The structurally characterised di-and tri-meric aminoalanes carrying substituents such as H, aryl and alkyl, respectively, have been synthesized mostly by elimination reactions. 3 Aminoalanes are generally the starting materials for the preparation of iminoalanes, which can adopt a multitude of different geometries in the solid state, namely rings, 4,5 chains, 6 cubes and more complex cages. 7, 8 Most of the compounds containing Al᎐N bonds are neutral; only a small number of them are positively charged.…”

mentioning

confidence: 99%

Synthesis and structure of an anionic aluminium–nitrogen compound containing a ladder-shaped core

Horchler¹,

Parisini²,

Roesky³

et al. 1997

J. Chem. Soc., Dalton Trans.

View full text Add to dashboard Cite

“…Downs et al, 1992;Schauer & Robinson, 1993;Dü michen et al, 1999;Tang et al, 2001;Dinnebier & Mü ller, 2003). Schauer & Robinson (1993) analyzed a number of molecular structures of aminoalanes and concluded that the molecular structure is a product of the interplay of electronic, steric and intermolecular forces owing to the packing in the crystal structure. Thus, these crystal structures are often built up from molecules formed by dimers or trimers, which are also formed in aminoboranes and aminogallanes (Fig.…”

Section: Introductionmentioning

confidence: 99%

Molecular structure of diethylaminoalane in the solid state: an X-ray powder diffraction, DFT calculation and Raman spectroscopy study

Bernert

Ley

Ruiz‐Fuertes

et al. 2016

Acta Crystallogr Sect B

View full text Add to dashboard Cite

The crystal structure of diethylaminoalane, [H2Al-N(C2H5)2]2, was determined by X-ray powder diffraction in conjunction with DFT calculations. Diethylaminoalane crystallizes in the monoclinic space group P21/c with a = 7.4020 (2), b = 12.9663 (3), c = 7.2878 (2) Å and β = 90.660 (2)° at 293 K. The crystal structure was confirmed by DFT calculations and Raman spectroscopy. The molecular structure of diethylaminoalane consists of dimers of [H2Al-N(CH2CH3)2] in which an Al2N2 four-membered ring is formed by a center of inversion. Such an arrangement of the aminoalane moieties in the crystal structure is well known for this class of compound, as shown by the comparison with ethylmethylaminoalane and diisopropylaminoalane.

show abstract

Aminoalane Dimers and Trimers. An Examination of Structural and Steric Trends

Cited by 33 publications

References 37 publications

Reaction of N,N′-bis(mesityl)ethylenediamine with triethylaluminium. Formation of ten-membered aluminium amide heterocycles

Reaction of N,N′-bis(mesityl)ethylenediamine with triethylaluminium. Formation of ten-membered aluminium amide heterocycles

Synthesis and structure of an anionic aluminium–nitrogen compound containing a ladder-shaped core

Molecular structure of diethylaminoalane in the solid state: an X-ray powder diffraction, DFT calculation and Raman spectroscopy study

Contact Info

Product

Resources

About