trans-Disubstituted diamido/diamine cyclam zirconium complexes

abstract

The reaction of H(2)[1,8-dibenzyl-1,4,8,11-tetraazacyclotetradecanel (H(2)Bn(2)CYclam) with 2 equiv of LiBu gives Li(2)Bn(2)Cyclam(L)2 (L = Et(2)O or THF) that reacts with ZrCl(4)(THF)(2) to afford (Bn(2)Cyclam)ZrCl(2) in 40% yield. Alternatively (Bn(2)Cyclam)ZrCl(2) may be obtained via ZrCl(2)(CH(2)SiMe(3))(2)(Et(2)O)(2) in a significantly higher yield (87%), avoiding the lithiation of H(2)Bn(2)Cyclam. The syntheses of other H(2)*Bn(2)CYClaM ligand precursors (*Bn = 3,5-dimethylbenzyl and 3,5-di(tert-butyl)benzyl) and the corresponding Zr derivatives ({3,5-Me(2)Bn}(2)-Cyclam)ZrCl(2) and ({3,5-(t)Bu(2)Bn}(2)-Cyclam)ZrCl(2) are also reported. Results on preliminary tests of E-caprolactone and ethylene polymerisation reactions are presented. (C) 2008 Elsevier B.V. All rights reserved.

keywords

OLEFIN POLYMERIZATION; TITANIUM COMPLEXES; HAFNIUM COMPLEXES; CHEMISTRY; CATALYSTS; LIGANDS; MACROCYCLES; CONTAIN

subject category

Chemistry

authors

Munha, RF; Alves, LG; Maulide, N; Duarte, MT; Marko, IE; Fryzuk, MD; Martins, AM

our authors

Groups

acknowledgements

We are grateful to Fundacao para a Ciencia e a Tecnologia, Portugal that funded this work (POCI/QUI/55744/2004 and SFRH/BD/29986/2006).

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