Expected and unexpected reactivities of homoleptic LiNacNac and heteroleptic NacNacMg(TMP) β-diketiminates towards various small unsaturated organic molecules

Gauld, Richard M. and Lynch, Jennifer R. and Kennedy, Alan R. and Barker, Jim and Reid, Jacqueline and Mulvey, Robert E. (2021) Expected and unexpected reactivities of homoleptic LiNacNac and heteroleptic NacNacMg(TMP) β-diketiminates towards various small unsaturated organic molecules. Inorganic Chemistry, 60 (8). pp. 6057-6064. ISSN 1520-510X (https://doi.org/10.1021/acs.inorgchem.1c00549)

[thumbnail of Mulvey-etal-IC-2021-Expected-and-unexpected-reactivities-of-homoleptic-LiNacNac]
Preview
 Text. Filename: Mulvey_etal_IC_2021_Expected_and_unexpected_reactivities_of_homoleptic_LiNacNac.pdf
Final Published Version
License: Creative Commons Attribution 4.0 logo
Download (1MB)| Preview

Abstract

Homoleptic LiNacNac forms simple donor-acceptor complexes with N,N′-dicyclohexylcarbodiimide (CyN= C= NCy), triphenylphosphine oxide (Ph3P= O), and benzophenone (Ph2CO). These crystallographically characterized compounds could be regarded as model intermediates en route to reducing the N= C, P= O, and C= O bonds of unsaturated substrates. Heteroleptic NacNacMg(TMP) intriguingly functions as a TMP nucleophile both with t-BuNCO and t-BuNCS, producing a urea or thiourea derivative respectively attached to Mg, though the NacNac ligand in the former reaction also engages noninnocently with a second t-BuNCO molecule via insertion at the reactive NacNac backbone γ-carbon site.

ORCID iDs

Gauld, Richard M., Lynch, Jennifer R., Kennedy, Alan R. ORCID logoORCID: https://orcid.org/0000-0003-3652-6015, Barker, Jim, Reid, Jacqueline and Mulvey, Robert E. ORCID logoORCID: https://orcid.org/0000-0002-1015-2564;
  • Item type:Article
    ID code:76010
    Dates:
    Date
    Event
    19 April 2021
    Published
    8 April 2021
    Published Online
    31 March 2021
    Accepted
    Subjects:Science > Chemistry
    Department:Faculty of Science > Pure and Applied Chemistry
    Depositing user: Pure Administrator
    Date deposited:01 Apr 2021 16:01
    Last modified:11 Nov 2024 13:02
    URI:https://strathprints.strath.ac.uk/id/eprint/76010
CORE (COnnecting REpositories)