Synthesis and reactivity of titanium(IV)-salen complexes containing oxygen and chloride ligands
The reaction of in situ-generated Ti(OiPr)2(X)2 (X = OAr, OTf) with H2salen or H2salen* yields the stable, well-characterized Ti(salen)X2 series of complexes. Ti(salen*)(OTf)2 could also be synthesized by reacting the previously unknown Ti(salen*)Cl2 with TMSOTf or AgOTf. The ditriflates could be converted back to the aryloxides upon reaction with 2 equiv of NaOAr. Ti(salen)(4-tert-butyphenoxy)2 was characterized by X-ray crystallography and found to contain a pseudoplanar salen ligand with two axially coordinated aryloxide ligands. H2salen and H2salen* were also found to cleanly react with in situ-generated Ti(OiPr)3(X) (X = OC(O)R, OTf) to yield the unsymmetrically substituted Ti(salen)(OiPr)(X) and Ti(salen*)(OiPr)(X) complexes, respectively. In the case of X = OTf, the isopropoxide ligand could be cleanly protonated with 4-fert-butylphenol to yield Ti(salen)(OAr)(OTf) in high yield. This complex could also be accessed by the comproportionation reaction of Ti(salen)(OAr)2 and Ti(salen)(OTf)2.
Chen, Huiyuan,White, Peter S.,Gagné, Michel R.
p. 5358 - 5366
(2008/10/08)
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