Neutral tridentate O,N,L-type ligands aeimp-H, quimp-H and ppimp-H (aeimp-H=2-((dimethylamino)ethylimino)methyl)-4,6-di-tert-butyl-phenol; quimp-H=2-((quinolin-8-ylimino)methyl)-4,6-di-tert-butyl-phenol; ppimp-H=2-((2-phenoxyphenylimino)methyl)-4,6-di-tert-butylphenol) readily reacted with AlMe2Cl to afford the corresponding methyl-chloro aluminium derivatives (aeimp)AlMeCl (2a) (quimp)AlMeCl (2b) and (ppimp)AlMeCl (2c) with concomitant elimination of methane. DFT calculations suggested that the pendant donor arm in these species is weakly bounded to the metal centre. A fast chloride abstraction by Me2AlCl from the neutral derivatives 2a and 2b produced the tetrahedral cationic species (O,N,L)AlMe+ counterbalanced by the Me2AlCl2 - anion. Analogously direct treatment of bpzmp-H (bpzmp-H=2,4-di-tert-butyl-6-(bis(3,5-dimethylpyrazol-1yl)methyl)phenol) with two equivalents of Me2AlCl afforded the Al cation [(bpzmp)AlMe][Me2AlCl2] (3d) as determined by single crystal X-ray analysis.

Reactivity studies of AlMe2Cl with potentially tridentate O,N,L-type ligands

GRISI, Fabia;MILIONE, Stefano
2014-01-01

Abstract

Neutral tridentate O,N,L-type ligands aeimp-H, quimp-H and ppimp-H (aeimp-H=2-((dimethylamino)ethylimino)methyl)-4,6-di-tert-butyl-phenol; quimp-H=2-((quinolin-8-ylimino)methyl)-4,6-di-tert-butyl-phenol; ppimp-H=2-((2-phenoxyphenylimino)methyl)-4,6-di-tert-butylphenol) readily reacted with AlMe2Cl to afford the corresponding methyl-chloro aluminium derivatives (aeimp)AlMeCl (2a) (quimp)AlMeCl (2b) and (ppimp)AlMeCl (2c) with concomitant elimination of methane. DFT calculations suggested that the pendant donor arm in these species is weakly bounded to the metal centre. A fast chloride abstraction by Me2AlCl from the neutral derivatives 2a and 2b produced the tetrahedral cationic species (O,N,L)AlMe+ counterbalanced by the Me2AlCl2 - anion. Analogously direct treatment of bpzmp-H (bpzmp-H=2,4-di-tert-butyl-6-(bis(3,5-dimethylpyrazol-1yl)methyl)phenol) with two equivalents of Me2AlCl afforded the Al cation [(bpzmp)AlMe][Me2AlCl2] (3d) as determined by single crystal X-ray analysis.
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11386/4121053
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