Structural Diversity in Lewis‐Base Complexes of Lithium Triflamide

Complexation of the salt lithium triflamide [LiNTf 2 ; NTf 2 = N(SO 2 CF 3 ) 2 ], with a range of nitrogen donor ligands results in the formation of a series of coordination complexes [(Tf 2 N)Li·N(H)PPh 2 Me] ( 1 ), [(Tf 2 N)Li·N(H)PPh 3 ] ( 2 ), [(Tf 2 N)Li·TMEDA] ( 3 ), [(Tf 2 N)Li·PMDTEA] ( 4 ) and [(Bz‐TAC) 2 Li][NTf 2 ] ( 5 ). The molecular structures of 1 , 3 , 4 and 5 have been determined by single‐crystal X‐ray diffraction. The resulting solvated structures are discussed in terms of solvent‐separated ion pairs, contact ion pairs and higher aggregates, with the degree of aggregation and ion contact being dependent on the relative coordinating abilities and steric demands of the donor ligand and the anion, and provide an insight into the possible structures of lithium aggregates present in complex systems such as polymer electrolytes and synthetic reaction media. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)