Donor-influenced structure-activity correlations in stoichiometric and catalytic reactions of lithium monoamido-monohydrido-dialkylaluminates

Lemmerz, Lara E. and McLellan, Ross and Judge, Neil R. and Kennedy, Alan R. and Orr, Samantha A. and Uzelac, Marina and Hevia, Eva and Robertson, Stuart D. and Okuda, Jun and Mulvey, Robert E. (2018) Donor-influenced structure-activity correlations in stoichiometric and catalytic reactions of lithium monoamido-monohydrido-dialkylaluminates. Chemistry - A European Journal, 24 (39). pp. 9940-9948. ISSN 1521-3765 (https://doi.org/10.1002/chem.201801541)

[thumbnail of Lemmerz_etal_CEJ_2018_Donor_influenced_structure_activity_correlations_in_stoichiometric_and_catalytic_reactions]
Preview
 Text. Filename: Lemmerz_etal_CEJ_2018_Donor_influenced_structure_activity_correlations_in_stoichiometric_and_catalytic_reactions.pdf
Final Published Version
License: Creative Commons Attribution 4.0 logo
Download (1MB)| Preview

Abstract

A series of heteroleptic monoamido-monohydrido dialkyl-aluminate complexes of general formula [iBu2AlTMPHLi·donor] are synthesized and characterised in the 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.

ORCID iDs

Lemmerz, Lara E., McLellan, Ross ORCID logoORCID: https://orcid.org/0000-0001-9700-0258, Judge, Neil R., Kennedy, Alan R. ORCID logoORCID: https://orcid.org/0000-0003-3652-6015, Orr, Samantha A. ORCID logoORCID: https://orcid.org/0000-0001-9295-9312, Uzelac, Marina ORCID logoORCID: https://orcid.org/0000-0002-5060-7017, Hevia, Eva ORCID logoORCID: https://orcid.org/0000-0002-3998-7506, Robertson, Stuart D. ORCID logoORCID: https://orcid.org/0000-0002-9330-8770, Okuda, Jun and Mulvey, Robert E. ORCID logoORCID: https://orcid.org/0000-0002-1015-2564;
CORE (COnnecting REpositories)