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 journalArticle

15 Citations (Scopus)

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.

LanguageEnglish
Pages9940-9948
Number of pages9
JournalChemistry - A European Journal
Volume24
Issue number39
Early online date26 Apr 2018
DOIs
Publication statusPublished - 11 Jul 2018

Fingerprint

hydroboration
constitution
Ketones
Lithium
ketones
lithium
aluminates
Pyrazines
Deprotonation
Triazoles
pyrazines
Aldehydes
aldehydes
insertion
reactivity
Metals
Ligands
solid state
ligands
metals

Keywords

  • stoichiometric transformations
  • catalytic transformations
  • metals
  • main group chemistry

Cite this

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title = "Donor-influenced structure-activity correlations in stoichiometric and catalytic reactions of lithium monoamido-monohydrido-dialkylaluminates",
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.",
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Donor-influenced structure-activity correlations in stoichiometric and catalytic reactions of lithium monoamido-monohydrido-dialkylaluminates. / Lemmerz, Lara E.; McLellan, Ross; Judge, Neil R.; Kennedy, Alan R.; Orr, Samantha A.; Uzelac, Marina; Hevia, Eva; Robertson, Stuart D.; Okuda, Jun; Mulvey, Robert E.

In: Chemistry - A European Journal, Vol. 24, No. 39, 11.07.2018, p. 9940-9948.

Research output: Contribution to journalArticle

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T1 - Donor-influenced structure-activity correlations in stoichiometric and catalytic reactions of lithium monoamido-monohydrido-dialkylaluminates

AU - Lemmerz, Lara E.

AU - McLellan, Ross

AU - Judge, Neil R.

AU - Kennedy, Alan R.

AU - Orr, Samantha A.

AU - Uzelac, Marina

AU - Hevia, Eva

AU - Robertson, Stuart D.

AU - Okuda, Jun

AU - Mulvey, Robert E.

PY - 2018/7/11

Y1 - 2018/7/11

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AB - 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.

KW - stoichiometric transformations

KW - catalytic transformations

KW - metals

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