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Low Valent Organoaluminum (+I, +II) Species

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Modern Organoaluminum Reagents

Part of the book series: Topics in Organometallic Chemistry ((TOPORGAN,volume 41))

Abstract

Since the isolation of the first stable molecular aluminum(II) compound {(Me3Si)2CH}2Al–Al{CH(SiMe3)2}2, the field of low oxidation state aluminum species has burgeoned tremendously. Organoaluminum(I) species (RAl) n stabilized with bulky substituents have been isolated and used as reducing agents, precursors to aluminum(III) compounds, ligands toward transition group metal complexes, and main group Lewis acids. Mixed valent aluminum compounds and numerous clusters such as the large aluminum anion [Al77{N(SiMe3)2}20]2− have provided insight into the stepwise formation of metallic aluminum from molecular precursors. It now appears likely that low oxidation state organoaluminum compounds will find their way into the organic and organometallic synthetic toolbox.

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Abbreviations

2e–2c:

Two electrons–two centers

Ar′:

2,6-Mes2C6H3

Bbp:

2,6-{(Me3Si)2CH}2C6H3

Cp:

Cyclopentadienide

Cp*:

Pentamethylcyclopentadienide

Cp′:

Tetramethylcyclopentadienide

Dipp:

2,6-(i-Pr)2C6H3

Dipp*:

2,6-(2,6-(i-Pr)2C6H3)2C6H3

Do:

Donor

EPR:

Electron paramagnetic resonance

HOMO:

Highest occupied molecular orbital

IDipp:

1,3-Di-(2,6-(i-Pr)2C6H2)imidazolin-2-ylidene

LUMO:

Lowest occupied molecular orbital

Mes:

Mesityl (=2,4,6-Me3C6H2)

Mes*:

2,4,6-(t-Bu)3C6H2

NHC:

N-heterocyclic carbene

NMR:

Nuclear magnetic resonance

THP:

Tetrahydropyran

TMEDA:

Tetramethylethylenediamine

Trip:

2,4,6-(i-Pr)3C6H2

UV/Vis:

Ultraviolet/visible

VT:

Variable temperature

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  1. Florida Institute of Technology, 150 W. University Blvd, Melbourne, FL, 32901, USA

    Rudolf J. Wehmschulte

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  1. Rudolf J. Wehmschulte
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Correspondence to Rudolf J. Wehmschulte .

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  1. , School of Chemistry, The University of Nottingham, University Park, Nottingham, NG7 2RD, United Kingdom

    Simon Woodward

  2. Laboratoire DECOMET, Institut Le Bel, Université de Strasbourg, 4 rue Blaise Pascal, Strasbourg, 67000, France

    Samuel Dagorne

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Wehmschulte, R.J. (2012). Low Valent Organoaluminum (+I, +II) Species. In: Woodward, S., Dagorne, S. (eds) Modern Organoaluminum Reagents. Topics in Organometallic Chemistry, vol 41. Springer, Berlin, Heidelberg. https://doi.org/10.1007/3418_2012_34

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