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

Crimmin, MR; Hill, MS; Hitchcock, PB; Mahon, MF; (2010) Synthesis of beta-diketiminato calcium silylamides and their reactions with triethylaluminium. NEW J CHEM , 34 (8) 1572 - 1578. 10.1039/c0nj00042f.

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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.

Type:Article
Title:Synthesis of beta-diketiminato calcium silylamides and their reactions with triethylaluminium
DOI:10.1039/c0nj00042f
Keywords:ALKALINE-EARTH METALS, STYRENE POLYMERIZATION, BENZYL COMPLEXES, INTRAMOLECULAR HYDROAMINATION, CATALYZED HYDROAMINATION, BENZYLCALCIUM COMPLEXES, LACTIDE POLYMERIZATION, ARYLCALCIUM HALIDES, THF SOLUTION, WELL
UCL classification:UCL > School of BEAMS > Faculty of Maths and Physical Sciences > Chemistry

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