223414-22-0Relevant academic research and scientific papers
Expected and Unexpected Reactivities of Homoleptic LiNacNac and Heteroleptic NacNacMg(TMP) β-Diketiminates toward Various Small Unsaturated Organic Molecules
Gauld, Richard M.,Lynch, Jennifer R.,Kennedy, Alan R.,Barker, Jim,Reid, Jacqueline,Mulvey, Robert E.
, p. 6057 - 6064 (2021)
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.
Salt metathesis as an alternative approach to access aluminium(i) and gallium(i) ?-diketiminates
G?rls, Helmar,Kretschmer, Robert,Kysliak, Oleksandr
supporting information, p. 6377 - 6383 (2020/06/03)
Salt metathesis,i.e.the reaction of sodium ?-diketiminate with (AlCp*)4and GaCp*, respectively, is a valuable pathway to access the respective aluminium(i) and gallium(i) ?-diketiminatesIandII. The protocol gives better yields compared to the established procedures and avoids the use of strong reducing agents such as metallic potassium. Furthermore, the aluminium(i) ?-diketiminateIwas found to react with itself and yields upon C-N bond cleavage and hydrogen-atom transfer the asymmetric dinuclear aluminium(iii) complexVthat is readily separated fromIby crystallisation. The reaction mechanism has been probed by means of DFT and DLPNO-CCSD(T) calculations and the computational findings are in good agreement with the experimental observations.
