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Issue 42, 2013
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Preparation and properties of a series of structurally diverse aluminium hydrides supported by β-diketiminate and bis(amide) ligands

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Abstract

The synthesis of a diverse series of hydride complexes of aluminium coordinated by N,N′-chelating ligands is reported. Reaction of [{2,6-iPr2C6H3}NC(Me)CHC(Me)N(H)CH2CH2NMe2] with either LiAlH4 or Me3N·AlH3 allows isolation of the corresponding five-coordinate aluminium dihydride [κ3-{(2,6-iPr2C6H3)NC(Me)CHC(Me)NCH2CH2NMe2}AlH2] (2). The latter complex demonstrates trigonal bipyramidal geometry in the solid-state. Correlation of solid and n-hexane solution infrared spectroscopy data reveals that this coordination is retained in solution. To evaluate the observed coordination geometry, the dissociation of the pendant ligand of 2 was investigated by DFT methods conducted with the M06-2X functional and a hybrid 6,31G+(d,p)/Lanl2DZ basis-set. Reaction of Me3N·AlH3 with both N,N′-bis(di-iso-propylphenyl)ethylenediamine and N,N′-bis(mesityl)ethylenediamine gave [{κ2-(ArNCH2)2}AlH(NMe3)] (Ar = Mes, 3a; Ar = 2,6-di-iso-propylphenyl, 3b) in moderate yields. Removal of NMe3 from 3b by heating under dynamic vacuum allowed the isolation of cis-[AlH{μ-N(Ar)CH2CH2N(Ar)}] (Ar = 2,6-di-iso-propylphenyl, cis-4b22) as a single diastereomer following crystallization. DFT studies in combination with infrared and NMR spectroscopy and single crystal X-ray diffraction data provide a weight of evidence consistent with the robust dimeric structure of cis-4b22 remaining intact in solution. An unusual reaction in which the aluminium dihydride, [κ2-{(2,6-Me2C6H3NHCH2)2CH}AlH2], promotes the P–C bond cleavage of Ph3PCH2 is also reported.

Graphical abstract: Preparation and properties of a series of structurally diverse aluminium hydrides supported by β-diketiminate and bis(amide) ligands

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Publication details

The article was received on 06 Aug 2013, accepted on 27 Aug 2013 and first published on 02 Sep 2013


Article type: Paper
DOI: 10.1039/C3DT52148F
Citation: Dalton Trans., 2013,42, 15199-15206
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    Preparation and properties of a series of structurally diverse aluminium hydrides supported by β-diketiminate and bis(amide) ligands

    A. E. Nako, S. J. Gates, A. J. P. White and M. R. Crimmin, Dalton Trans., 2013, 42, 15199
    DOI: 10.1039/C3DT52148F

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