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Exploiting σ/π Coordination Isomerism to Prepare Homologous Organoalkali Metal (Li, Na, K) Monomers with Identical Ligand Sets
Author(s) -
Davidson Matthew G.,
GarciaVivo Daniel,
Kennedy Alan R.,
Mulvey Robert E.,
Robertson Stuart D.
Publication year - 2011
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201003493
Subject(s) - delocalized electron , chemistry , monomer , metal , lithium (medication) , ligand (biochemistry) , crystallography , ion , derivative (finance) , coordination complex , potassium , stereochemistry , sodium , inorganic chemistry , organic chemistry , medicine , biochemistry , receptor , financial economics , economics , endocrinology , polymer
Tetraamine Me 6 TREN has been used as a scaffold support to provide coordinative saturation in the complexes PhCH 2 M⋅Me 6 TREN (M=Li, Na, K). The Li derivative displays a LiC σ interaction with a pyramidalized CH 2 both in the solid state and in solution, and represents the first example of η 4 coordination of Me 6 TREN to lithium. In the sodium derivative, the metal cation slips slightly towards the delocalized π electrons whilst maintaining a partial σ interaction with the CH 2 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.