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.
Highlights
When attached to organic ligands, lithium and magnesium represent the luminaries of the s-block of the periodic table, arguably of the whole of the periodic table, in terms of their phenomenal synthetic utility
Of note is work by Lichtenberg, who structurally characterized a lithium aminotroponiminate (LiATI) solvated by Ph3PO, exhibiting a Li chelated by two ATI N atoms in a similar arrangement to that of 2 but with an additional O (THF) ligation.[54]
We have demonstrated that there remains a significant and wide variety of potential reactivities of homoleptic LiNacNac and heteroleptic NacNacMg(TMP) β-diketiminates toward small unsaturated molecules that are yet to be fully explored
Summary
When attached to organic ligands, lithium and magnesium represent the luminaries of the s-block of the periodic table, arguably of the whole of the periodic table, in terms of their phenomenal synthetic utility. Of note is work by Lichtenberg, who structurally characterized a lithium aminotroponiminate (LiATI) solvated by Ph3PO, exhibiting a Li chelated by two ATI N atoms in a similar arrangement to that of 2 but with an additional O (THF) ligation.[54] Significantly, a search of the CSD revealed no hits for a phosphine oxide unit bonded to LiNacNac, with the closest match being a 1,8-C10H6{NHSiMe3}2-supported dilithium compound; the lack of delocalization over the backbone of this ligand limits comparison.[55] Attempted reactions with the sulfur analogue Ph3P S failed to produce a complex with LiNacNac as determined via NMR studies, contrasting with Nikonov’s report of NacNacAl(I) which forms NacNacAl( S)S PPh3 via a complexation/oxidative cleavage process.[56]. These lengths suggest considerable delocalization within this NC(NTMP)S unit ( across S1−C39−N3), which adopts a thiourea-like arrangement
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