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 0020-1669

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    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;