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RESEARCH ARTICLE
Contents Vol 67(7)

Preparation and Structural Studies of Non-Symmetric Guanidinate-Supported Zirconium Complexes

Rafael Fernández-Galán A B , Juan-Antonio Navarro A , Fernando Carrillo-Hermosilla A B , Antonio Antiñolo A , Isabel López-Solera A and Elena Villaseñor A
+ Author Affiliations
- Author Affiliations

A Departamento de Química Inorgánica, Orgánica y Bioquímica, Facultad de Ciencias y Tecnologías Químicas, Universidad de Castilla-La Mancha, Campus Universitario, Ciudad Real, 13071-Spain.

B Corresponding authors. Email: rafael.fgalan@uclm.es; fernando.carrillo@uclm.es

Australian Journal of Chemistry 67(7) 1063-1070 https://doi.org/10.1071/CH14181
Submitted: 28 March 2014  Accepted: 26 May 2014   Published: 16 June 2014

Abstract

The new lithium guanidinate salt [Li{μ-κ1,κ2,N,N′-(NEt)(N-t-Bu)CNMe2}(THF)]2 (1) was obtained by the reaction of HNMe2 with n-BuLi and further reaction with the asymmetric carbodiimide EtN=C=N-t-Bu. Guanidinate-supported zirconium complexes [Zr{κ2,N,N′-(NEt)(N-t-Bu)CNMe2}(μ-Cl)Cl2]2 (2), [Zr{κ2,N,N′-(NEt)(N-t-Bu)CNMe2}3Cl] (4), [Zr{κ2,N,N′-(NEt)(N-t-Bu)CNMe2}2(η5-C5H5)Cl] (5) and [Zr{κ2,N,N′-(NEt)(N-t-Bu)CNMe2}(η5-C5H5)2Cl] (6) were prepared. Complexes 2, 4, and 6 were synthesized by the metathesis reaction of ZrCl4 or [ZrCl2(η5-C5H5)2] with 1. The previously described complex [Zr{κ2,N,N′-(NEt)(N-t-Bu)CNMe2}2Cl2] (3), which was prepared by the insertion reaction of EtN=C=N-t-Bu into a metal–amido bond of [Zr(NMe2)2Cl2(THF)2], allowed the new complex 5 to be obtained by reaction with NaC5H5. All of the new complexes were characterized spectroscopically and the molecular structures of 1, 4, and 6 were determined by single-crystal X-ray diffraction.


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