Expected and Unexpected Reactivities of Homoleptic LiNacNac and Heteroleptic NacNacMg(TMP) β-Diketiminates toward Various Small Unsaturated Organic Molecules

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, C═O bonds of unsaturated substrates. Heteroleptic NacNacMg(TMP) intriguingly functions a TMP nucleophile both t-BuNCO t-BuNCS, producing urea or thiourea derivative respectively attached Mg, though NacNac ligand in former reaction also engages noninnocently second molecule via insertion at reactive backbone γ-carbon site.