TY - JOUR
T1 - The first trimetallic lithium-sodium-potassium complex
T2 - Synthesis and crystal structure of a twelve-vertex Li2Na2K2N4O2 cage molecule containing an amide-alkoxide combination
AU - Mackenzie, F.M.
AU - Mulvey, Robert
AU - Clegg, W.
AU - Horsburgh, Lynne
PY - 1996/5/15
Y1 - 1996/5/15
N2 - Several molecular complexes containing a mixture of two alkali metals (e.g., lithium−sodium and lithium−potassium) have been characterised by X-ray crystallographic studies over the past decade.1 Here, in this paper, we break new ground in this important area of intermetallic chemistry by reporting the successful synthesis and X-ray crystallographic characterization of an unprecedented trimetallic (lithium−sodium−potassium) formulation. Furthermore, the new complex, [{[PhN(H)]2(t-BuO)LiNaK·(TMEDA)2}2], (1), is closely related to the cocompositions currently employed as “superbases”,2 reagents of boosted deprotonating ability, in organic synthesis. Two recently reported crystal structures regarded to be architectural models for superbases, a carbanion−alkoxide3a and a carbanion−amide3b combination, both contain their two anionic functionalities (C-/RO- and C-/R2N-, respectively) within one ligand. On the other hand, more realistically, 1 contains two distinct types of anionic ligand [amide−alkoxide (R2N-/RO-)]4 as is the case in superbase reagents.2
AB - Several molecular complexes containing a mixture of two alkali metals (e.g., lithium−sodium and lithium−potassium) have been characterised by X-ray crystallographic studies over the past decade.1 Here, in this paper, we break new ground in this important area of intermetallic chemistry by reporting the successful synthesis and X-ray crystallographic characterization of an unprecedented trimetallic (lithium−sodium−potassium) formulation. Furthermore, the new complex, [{[PhN(H)]2(t-BuO)LiNaK·(TMEDA)2}2], (1), is closely related to the cocompositions currently employed as “superbases”,2 reagents of boosted deprotonating ability, in organic synthesis. Two recently reported crystal structures regarded to be architectural models for superbases, a carbanion−alkoxide3a and a carbanion−amide3b combination, both contain their two anionic functionalities (C-/RO- and C-/R2N-, respectively) within one ligand. On the other hand, more realistically, 1 contains two distinct types of anionic ligand [amide−alkoxide (R2N-/RO-)]4 as is the case in superbase reagents.2
KW - tert butoxide
KW - stack
KW - alkali metals
U2 - 10.1021/ja960327t
DO - 10.1021/ja960327t
M3 - Article
SN - 0002-7863
VL - 118
SP - 4721
EP - 4722
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 19
ER -