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DOI: 10.1039/A901666J (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1999, 2853-2859

Zirconium mixed ligand isopropoxide/aminoalkoxide complexes: crystal structures of [Zr2(OPri)6(L)2] and [Zr2(OBut)3(bdmap)4(OH)] {where L = dmap, 1-dimethylaminopropan-2-olate and bdmap, 1,1-bis(dimethylamino)propan-2-olate}

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Kirsty A. Fleeting, Paul O’Brien, Anthony C. Jones, David J. Otway, Andrew J. P. White and David J. Williams

Abstract

The reactions of the homoleptic zirconium alkoxides [Zr2(OPri)8(PriOH)2] and Zr(OBut)4 in n-hexane suspensions or solutions with two equivalents of the aminoalcohols 2-dimethylaminoethanol (Hdmae), 1-dimethylaminopropan-2-ol (Hdmap), or 1,1-bis(dimethylamino)propan-2-ol (Hbdmap) have been studied. Products with the formula [Zr(OR)2(dmae)2] (R = Pri 1 or But 2), [Zr2(OPri)6(L)2] (L = dmap 3 or bdmap 4), and [Zr2(OBut)3(bdmap)4(OH)] 5 have been isolated. Compounds 3 and 4 have been shown by single crystal X-ray crystallography to be asymmetric binuclear complexes in the solid state. The two metal centres are bridged via the two aminoalkoxide oxygen atoms and one isopropoxide ligand. The remaining co-ordination spheres of the binuclear molecules are completed by 3 terminal isopropoxide ligands on one metal centre, and 2 terminal isopropoxide ligands on the other. Compound 5 was found to be binuclear, but instead of a µ-isopropoxide bridge a µ-OH group was observed which intramolecularly hydrogen bonds to one of the free NMe2 groups on a terminal bdmap ligand. The remaining sites in the co-ordination spheres are filled by 3 terminal tert-butoxide ligands on one metal centre and two terminal aminoalkoxide ligands on the other. These are the first binuclear 6/7 co-ordinate zirconium compounds. The structural studies are helpful in understanding the behaviour of these and related complexes as precursors in the MOCVD of ZrO2 films.

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