Synthesis, characterization, and reactivity of organometallic Zr(IV) carboxylate complexes
1998; Elsevier BV; Volume: 270; Issue: 1-2 Linguagem: Inglês
10.1016/s0020-1693(97)06117-3
ISSN1873-3255
AutoresDietrich Steinhuebel, Peter Fuhrmann, Stephen J. Lippard,
Tópico(s)Coordination Chemistry and Organometallics
ResumoA series of zirconium(IV) complexes, [ZrX2(XDK)], where XDK is the constrained carboxylate ligand m-xylylenediamine bis(Kemp's triacid imide), were prepared and structurally characterized. The solid state structure of the mononuclear carboxylate alkyl complex [Zr(CH2Ph)2(XDK)] reveals that one benzyl group is bonded in an η2-fashion to the metal center. The reactivity of [Zr(CH2Ph)2(XDK)] displays its electrophilic character toward nucleophiles strong enough to displace the η2-benzyl group. Thus, weak sigma donor ligands such as CO, alkynes and anilines do not react, whereas strong sigma donors, such as pyridines and isocyanides, rapidly form the monoadduct [Zr(CH2Ph)2(4-tert-butylpyridine)(XDK)] and [Zr{η2-2,6-Me2PhNCCH2Ph}2(XDK)], an η2-iminoacyl derivative, respectively. Attempts to prepare zirconium amido complexes with H2XDK generally afforded the eight-coordinate [Zr(XDK)2] complex but use of the small amido ligand precursorZr(NMe2)4 allowed [Zr(NMe2)2(4-tert-butylpyridine)(XDK)] to be isolated in good yield.
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