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Triamidoamine chemistry of zirconium
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UNSPECIFIED (1999) Triamidoamine chemistry of zirconium. ORGANOMETALLICS, 18 (22). pp. 4608-4613. ISSN 0276-7333.
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Abstract
The reactions of H-3(NN3') (NN3' = N((CH2CH2NSiBuMe2)-Me-t)(3)) with [Zr(CH2Ph)(4)] and [Zr(NMe2)(4)] give the azazirconatranes [Zr(NN3')(CH2Ph)] and [Zr(NN3')(NMe2)], respectively. The reaction of [Li-3(NN3')(THF)(3)] with [ZrCl4(THF)(2)] fails to yield [Zr(NN3')Cl] cleanly, but this compound is accessible by reaction of [Zr(NN3')(CH2Ph)] with BCl3 or of [Zr(NN3')(NMe2)] with SiMe3Cl. The molecular structures of [Zr(NN3')X] (X = CH2Ph, NMe2, Cl) show that the triamidoamine ligands adopt the usual S-fold symmetric arrangement to give approximately trigonal-bipyramidal complexes. Attempted sublimation of [Zr(NN3')(CH2Ph)] or its treatment with Ha leads to clean conversion to the metallacyclic complex [Zr{N((CH2CH2NSiBuMe2)-Me-t)(2)(CH2CH2NSiBuMeCH2)-Me-t}] via deprotonation of a silylmethyl group and elimination of toluene. The molecular structure of this complex contrasts with those above in that the tert-butyldimethylsilyl groups adopt an upright conformation as a consequence of the presence of the metallacyclic unit. The dihedral angles N-ax-Zr-N-eq-Si are in the range 173.8-177.2 degrees. Exposure of the metallacycle to D-2 gas leads to deuteration of all three Me2Si groups via sequential deuteriolysis/sigma-bond metathesis. The less acidic (BuSi)-Bu-t and backbone CH2 groups are unaffected.
Item Type: | Journal Article | ||||
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Subjects: | Q Science > QD Chemistry | ||||
Journal or Publication Title: | ORGANOMETALLICS | ||||
Publisher: | AMER CHEMICAL SOC | ||||
ISSN: | 0276-7333 | ||||
Official Date: | 25 October 1999 | ||||
Dates: |
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Volume: | 18 | ||||
Number: | 22 | ||||
Number of Pages: | 6 | ||||
Page Range: | pp. 4608-4613 | ||||
Publication Status: | Published |
Data sourced from Thomson Reuters' Web of Knowledge
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