Kremer, Thomas; Harder, Sjoerd; Junge, Michael; Schleyer, Paul von Rague:

Mixed Aggregates of Alkali Metal Compounds: Structure and Stability of \"Superbase\" Models.

In: Organometallics, Jg. 15 (1996) ; Nr. 2, S. 585-595
ISSN: 0276-7333
Zeitschriftenaufsatz / Fach: Chemie
This ab initio study of the structure and stability of mixed alkali metal dimers models the transmetalation reactions which may lead to \"superbasic reagents\". Such reagents are mixts. of RLi and MOR' (M = Na-Cs) and show strongly enhanced metalating power. The possible existence of mixed dimers RM/LiOR' (M = Li-Cs, R = H, CH3, NH2, OH, F, and R' = H) has been evaluated at reasonably high levels of ab initio theory by MP2 calcns., using the pseudopotential method for the heavier alkali metals (K-Cs) and the 6-311+G** basis set for all other elements. Structures and energies of dimeric aggregates resulting from possible transmetalation reactions (metal exchange, anion exchange, anion and cation exchange and complete transmetalation) are calcd. and compared. In almost every case, mixed aggregates are more stable than other possible combinations. The driving force favoring such mixed aggregates is the formation of stronger Li bonds and the redn. of electrostatic metal-metal repulsion. Addnl. BECKE3LYP calcns. on the (MOH)2/(LiCH3)2 (M = Na, K) equil. using the 6-311+G* basis sets for H, C, O, Li, and Na, as well as pseudopotentials for K were performed on the RHF optimized geometries. One O(CH3)2 mol. on each of the metals decreases the differences in the relative stabilities of mixed aggregates and transmetalated compds., relative to the unsolvated equil.