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Benzyl Complexes of the Heavier Alkaline-Earth Metals: The First Crystal Structure of a Dibenzylstrontium Complex

2001; American Chemical Society; Volume: 20; Issue: 22 Linguagem: Inglês

10.1021/om010444j

1520-6041

F. Feil, Sjoerd Harder,

Synthesis and characterization of novel inorganic/organometallic compounds

The first benzylstrontium complex, di(2-Me2N-α-Me3Si-benzyl)strontium, has been prepared via reaction of the benzylpotassium complex with SrI2. The crystal structure of the bis(THF)-solvate complex shows hexacoordination at Sr. Structural analyses and NMR analyses of the related Li, K, and Ca complexes reveal that the delocalization of the negative charge in the phenyl ring is metal dependent and decreases along the row K > Li ≥ Sr > Ca. The presented benzylstrontium complex contains two chiral benzylic centers and forms diastereomers. In apolar solvents at room temperature both diastereomers are observed. Either higher temperatures or extra added THF ligands result in fast inversion of the chiral benzylic carbanion. The process is concentration independent and follows a dissociative mechanism in which one of the Sr−Cα bonds is broken. The chiral benzylic carbon atom in the strontium complex shows faster inversion than that in the analogue benzylcalcium complex (Ca, 0.07 M, ΔG⧧(60 °C) = 16.8 kcal mol-1; Sr, 0.08 M, ΔG⧧(30 °C) = 15.0 kcal mol-1). The new benzylstrontium complex is an active initiator for the anionic living polymerization of styrene and is more reactive than its Ca analogue.