Synthesis of β-diketiminato calcium silylamides and their reactions with triethylaluminium

M R Crimmin, Michael Hill, P B Hitchcock, Mary F Mahon

Research output: Contribution to journalArticle

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Abstract

Reaction of the beta-diketiminato calcium amide [{ArNC(Me)CHC(Me)NAr}Ca{N(SiMe3)(2)}(OEt2)] (Ar = 2,6-di-iso-propylphenyl) with triethylaluminium yields a novel calcium aluminate complex, [kappa(3)-{ArNC(Me)C(AlEt3)HC(Me)NAr}Ca{Et4Al}], in which coordination at calcium is provided by not only bridging interactions with the ethyl groups of the aluminate anion but also a tripodal kappa(3)-N,N,C-coordinated ligand derived from further reaction of the 'spectator' beta-diketiminate ligand with triethylaluminium. In the solid state, this compound exists as a 1 : 1 mixture of coordination isomers in which the Et4Al anion binds to calcium via either mu(2)- or mu(3)-coordination modes. Although persistent, and rapidly interconverting, at room temperature in solution, variable temperature NMR studies suggest that these two isomers undergo dissociative loss of triethylaluminium from the diketiminate ligand at low temperature.
LanguageEnglish
Pages1572-1578
Number of pages7
JournalNew Journal of Chemistry
Volume34
Issue number8
DOIs
StatusPublished - Aug 2010

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Calcium
Ligands
Isomers
Anions
Negative ions
Amides
Temperature
Nuclear magnetic resonance
triethylaluminum
calcium aluminate

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Synthesis of β-diketiminato calcium silylamides and their reactions with triethylaluminium. / Crimmin, M R; Hill, Michael; Hitchcock, P B; Mahon, Mary F.

In: New Journal of Chemistry, Vol. 34, No. 8, 08.2010, p. 1572-1578.

Research output: Contribution to journalArticle

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abstract = "Reaction of the beta-diketiminato calcium amide [{ArNC(Me)CHC(Me)NAr}Ca{N(SiMe3)(2)}(OEt2)] (Ar = 2,6-di-iso-propylphenyl) with triethylaluminium yields a novel calcium aluminate complex, [kappa(3)-{ArNC(Me)C(AlEt3)HC(Me)NAr}Ca{Et4Al}], in which coordination at calcium is provided by not only bridging interactions with the ethyl groups of the aluminate anion but also a tripodal kappa(3)-N,N,C-coordinated ligand derived from further reaction of the 'spectator' beta-diketiminate ligand with triethylaluminium. In the solid state, this compound exists as a 1 : 1 mixture of coordination isomers in which the Et4Al anion binds to calcium via either mu(2)- or mu(3)-coordination modes. Although persistent, and rapidly interconverting, at room temperature in solution, variable temperature NMR studies suggest that these two isomers undergo dissociative loss of triethylaluminium from the diketiminate ligand at low temperature.",
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