SOLID-STATE STRUCTURES AND DYNAMIC SOLUTION EQUILIBRIA OF BIS(DIBENZYLAMIDO)MAGNESIUM COMPLEXES - AGGREGATION DEPENDENCE ON STOICHIOMETRY AND DENTICITY OF DONOR SOLVENT
W. Clegg et al., SOLID-STATE STRUCTURES AND DYNAMIC SOLUTION EQUILIBRIA OF BIS(DIBENZYLAMIDO)MAGNESIUM COMPLEXES - AGGREGATION DEPENDENCE ON STOICHIOMETRY AND DENTICITY OF DONOR SOLVENT, Inorganic chemistry, 36(27), 1997, pp. 6238-6246
Reaction of commercial Bu2Mg with 2 molar equiv of dibenzylamine gives
the bis(amido)magnesium complex [{{(PhCH2)(2)N}(2)Mg}(2)], 1 Compound
1 is dimeric with three-coordinate magnesium in the crystalline state
. Addition of 2 molar equiv of the monodentate donor solvents THF and
HMPA to solutions of 1 affords the complexes [{{(PhCH2)(2)N}(2)Mg . TH
F}(2)], 2, and [{{(PhCH2)(2)N}(2)Mg . HMPA}(2)], 4 respectively, which
maintain the dimeric framework but increase the metal's coordination
number to 4. Addition of 3 molar equiv of HMPA, or a 20-fold excess, o
f THF to 1 causes deaggregation of the dimer to the monomeric bis-solv
ates [{{PhCH2)(2)N}(2)-Mg . 2THF], 3, and [{{PhCH2)(2)N}(2)Mg . 2HMPA]
, 5. The chelating ligand TMEDA gives the monomer [{(PhCH2)(2)N}(2)Mg
. TMEDA], 6, on mixing with 1. H-1 and C-13 NMR spectroscopic studies
reveal that dimer 1 is partially retained in arene solution but is in
equilibrium with the unsolvated monomer [{{PhCH2)(2)N}(2)Mg], 7. Conce
ntration studies on solutions of monosolvated dimer 3 show it to be in
equilibrium with both the bis-solvated monomer 5 and the unsolvated m
onomer 7. X-ray crystallographic determinations have been carried out
on complexes 1, 2, and 4-6, and a comparative analysis of their struct
ures is detailed. The bis(dibenzylamido)magnesium system has shown rem
arkable structural flexibility with di-, tri-, and tetracoordination a
t the metal.