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
Subjects:	Q Science > QD Chemistry
Journal or Publication Title:	ORGANOMETALLICS
Publisher:	AMER CHEMICAL SOC
ISSN:	0276-7333
Date:	25 October 1999
Volume:	18
Number:	22
Number of Pages:	6
Page Range:	pp. 4608-4613
Publication Status:	Published
URI:	http://wrap.warwick.ac.uk/id/eprint/13982

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