Ligand coordination modulates reductive elimination from aluminium(iii).

Stephanie J Urwin,David M Rogers,Michael J Cowley,Gary S Nichol

doi:10.1039/c6dt02698b

Stephanie J Urwin, David M Rogers + Show 2 more

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https://doi.org/10.1039/c6dt02698b

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Abstract

Oxidative addition of inert bonds at low-valent main-group centres is becoming a major class of reactivity for these species. The reverse reaction, reductive elimination, is possible in some cases but far rarer. Here, we present a mechanistic study of reductive elimination from Al(iii) centres and unravel ligand effects in this process. Experimentally determined activation and thermodynamic parameters for the reductive elimination of Cp*H from Cp*2AlH are reported, and this reaction is found to be inhibited by the addition of Lewis bases. We find that C-H oxidative addition at Al(i) centres proceeds by initial protonation at the low-valent centre.

Highlights

Oxidative addition of inert bonds at low-valent main-group centres is becoming a major class of reactivity for these species
We find that C–H oxidative addition at Al(I) centres proceeds by initial protonation at the low-valent centre
The facility with which transition metal systems can undergo reversible oxidative addition and reductive elimination reactions is central to their widespread applications in catalysis

Summary

Introduction

Oxidative addition of inert bonds at low-valent main-group centres is becoming a major class of reactivity for these species. Ligand coordination modulates reductive elimination from aluminium(III)† We present a mechanistic study of reductive elimination from Al(III) centres and unravel ligand effects in this process.

Results

Conclusion