Donor-influenced Structure–Activity Correlations in Stoichiometric and Catalytic Reactions of Lithium Monoamido-Monohydrido-Dialkylaluminates

Lara E. Lemmerz, Ross McLellan, Neil R. Judge, Alan R. Kennedy, Samantha A. Orr, Marina Uzelac, Eva Hevia, Stuart D. Robertson, Jun Okuda, Robert E. Mulvey

Research output: Contribution to journalArticlepeer-review

49 Citations (SciVal)

Abstract

A series of heteroleptic monoamido-monohydrido-dialkylaluminate complexes of general formula [iBu2AlTMPHLi⋅donor] were synthesized and characterised in solution and in the solid state. Applying these complexes in catalytic hydroboration reactions with representative aldehydes and ketones reveals that all are competent, however a definite donor substituent effect is discernible. The bifunctional nature of the complexes is also probed by assessing their performance in metallation of a triazole and phenylacetylene and addition across pyrazine. These results lead to an example of phenylacetylene hydroboration, which likely proceeds via deprotonation, rather than insertion as observed with the aldehydes and ketones. Collectively, the results emphasise that reactivity is strongly influenced by both the mixed-metal constitution and mixed-ligand constitution of the new aluminates.

Original languageEnglish
Pages (from-to)9940-9948
Number of pages9
JournalChemistry - A European Journal
Volume24
Issue number39
DOIs
Publication statusPublished - 11 Jul 2018

Bibliographical note

Funding Information:
The authors thank the EPSRC (grant award EP/N011384/1, DTP studentship to S.A.O., and vacation bursary to N.R.J.) and George Fraser (scholarship to S.A.O.) for their generous sponsorship of this research. REM thanks the Alexander von Humboldt foundation for a Humboldt Research Award. L. E. L. is grateful to the Deutscher Akademischer Austauschdienst (DAAD) for a research fellowship. The dataset underlying this research can be located at https://doi.org/10.15129/5fc161a9-08a7-4bd5-839a-164fa5660576.

Keywords

  • aluminate
  • homogeneous catalysis
  • hydroboration
  • lithium
  • metallation

ASJC Scopus subject areas

  • Catalysis
  • Organic Chemistry

Fingerprint

Dive into the research topics of 'Donor-influenced Structure–Activity Correlations in Stoichiometric and Catalytic Reactions of Lithium Monoamido-Monohydrido-Dialkylaluminates'. Together they form a unique fingerprint.

Cite this