Modification of a common β-diketiminate NacNac framework via sequential lithiation and small molecule insertion

Tools

Lynch, Jennifer R. and Kennedy, Alan R. and Barker, Jim and Mulvey, Robert E. (2024) Modification of a common β-diketiminate NacNac framework via sequential lithiation and small molecule insertion. Chemistry - A European Journal, 30 (15). e202303373. ISSN 1521-3765 (https://doi.org/10.1002/chem.202303373)

[thumbnail of Lynch-etal-CAEJ-2023-Modification-of-a-common-B-diketiminate-NacNac]
Preview
 Text. Filename: Lynch-etal-CAEJ-2023-Modification-of-a-common-B-diketiminate-NacNac.pdf
Final Published Version
License: Creative Commons Attribution 4.0 logo
Download (2MB)| Preview

Abstract

A widely utilised class of ligands in synthesis and catalysis, β-diketiminate (BDI) or NacNac compounds were initially considered innocent in the sense that they remained intact in all their applications. That changed when the γ-C−H unit of their NCCCN backbone was found to engage in reactions with electrophiles. Here, we show that this special reactivity can be used advantageously to prepare tripodal modifications of the common NacNac ligand derived from 2,6-diisopropylphenyl-β-methyldiketimine [NacNacH (Me, Dipp)]. Lithiation to give NacNacLi, followed by reactions with isocyanates, isothiocyanates and a carbodiimide, have afforded a series of tripodal NacNac variants having N,N,N,O; N,N,N,S; or N,N,N,N potential dentation sites, many of which have been crystallographically characterised. Distinct ligating modes of these new ligands have been elucidated through the crystal structures of their lithiated derivatives.

ORCID iDs

Lynch, Jennifer R., Kennedy, Alan R. ORCID logoORCID: https://orcid.org/0000-0003-3652-6015, Barker, Jim and Mulvey, Robert E. ORCID logoORCID: https://orcid.org/0000-0002-1015-2564;
  • Item type:Article
    ID code:87599
    Dates:
    Date
    Event
    12 March 2024
    Published
    30 November 2023
    Published Online
    30 November 2023
    Accepted
    13 October 2023
    Submitted
    Subjects:Science > Chemistry
    Department:Faculty of Science > Pure and Applied Chemistry
    Depositing user: Pure Administrator
    Date deposited:12 Dec 2023 14:53
    Last modified:15 Dec 2024 01:41
    URI:https://strathprints.strath.ac.uk/id/eprint/87599
CORE (COnnecting REpositories)