35090-00-7Relevant academic research and scientific papers
Exploiting σ/π coordination isomerism to prepare homologous organoalkali metal (Li, Na, K) monomers with identical ligand sets
Davidson, Matthew G.,Garcia-Vivo, Daniel,Kennedy, Alan R.,Mulvey, Robert E.,Robertson, Stuart D.
, p. 3364 - 3369 (2011)
Tetraamine Me6TREN has been used as a scaffold support to provide coordinative saturation in the complexes PhCH2M· Me6TREN (M=Li, Na, K). The Li derivative displays a Li-C σ interaction with a pyramidalized CH2 both in the solid state and in solution, and represents the first example of I·4 coordination of Me6TREN to lithium. In the sodium derivative, the metal cation slips slightly towards the delocalized π electrons whilst maintaining a partial σ interaction with the CH2 group. For the potassium case, coordinative saturation successfully yields the first monomeric benzylpotassium complex, in which the anion binds to the metal cation exclusively through its delocalized π system resulting in a planar CH 2 group. Easy as pi: Me6TREN acts as a coordinatively saturating scaffold for the complexes PhCH2M (M=Li, Na, K). As the size of the alkali metal increases, the solvated metal cation gradually slips from the lateral 'carbanionic' carbon to the aromatic π system, enabling the complex to maintain its monomeric constitution. Me6TREN=tris(N,N- dimethyl-2-aminoethyl)amine. Copyright
