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Issue 2, 1998
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Synthesis of new adducts and co-ordination complexes of zirconium and titanium containing β-aminoketone ligands. Crystal structures of isostructural adducts MCl4·2PriHNCMe[double bond, length half m-dash]CHCMe[double bond, length half m-dash]O (M = Ti or Zr) and the complex [Zr(PhNCMe[double bond, length half m-dash]CHCMe[double bond, length half m-dash]O)2Cl2]

Abstract

The reaction of MCl4 (M = Zr or Ti) with β-aminoketones HL (R1HNCR2[double bond, length half m-dash]CHCR3[double bond, length half m-dash]O; R2 = R3 = Me; R2 = Me, R3 = CF3) yielded the bis(ligand) adducts MCl4·2HL (M = Zr, R1 = Pri or Ph; R2 = R3 = Me; or R1 = Pri, R2 = Me, R3 = CF3; M = Ti, R1 = Pri or CH2CH[double bond, length half m-dash]CH2, R2 = R3 = Me). Reaction of MCl4 with the alkali-metal salts of the β-aminoketone ligands yielded the bis(ligand) complexes [M(R1NCMe[double bond, length half m-dash]CHCMe[double bond, length half m-dash]O)2Cl2] (M = Zr, R1 = Ph, p-ClC6H4, p-MeOC6H4 or Pri; M = Ti, R1 = Ph or p-MeOC6H4). Crystal structure determinations of the isostructural compounds ZrCl4·2PriHNCMe[double bond, length half m-dash]CHCMe[double bond, length half m-dash]O and TiCl4·2PriHNCMe[double bond, length half m-dash]CHCMe[double bond, length half m-dash]O indicated an octahedral co-ordination environment around the metal with the trans monodentate N–O ligands bound through the oxygen only. Strong intramolecular hydrogen bonding of the hydrogen on the nitrogen with the ligand oxygen is consistent with a ligand immonium enolate structure. An X-ray study of the octahedral complex [Zr(PhNCMe[double bond, length half m-dash]CHCMe[double bond, length half m-dash]O)2Cl2] indicated that the oxygens of the chelating N–O ligands are trans to each other and the chloride ligands are in a cis arrangement. The plane of one N–O chelate is in the equatorial plane of the complex and the plane of the second N–O ligand is at right angles to the first. The ligand forms a predominantly delocalised chelate ring but some ene–imine structure is apparent.

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J. Chem. Soc., Dalton Trans., 1998, 255-262
Article type
Paper

Synthesis of new adducts and co-ordination complexes of zirconium and titanium containing β-aminoketone ligands. Crystal structures of isostructural adducts MCl4·2PriHNCMe[double bond, length half m-dash]CHCMe[double bond, length half m-dash]O (M = Ti or Zr) and the complex [Zr(PhNCMe[double bond, length half m-dash]CHCMe[double bond, length half m-dash]O)2Cl2]

D. Jones, A. Roberts, K. Cavell, W. Keim, U. Englert, B. W. Skelton and A. H. White, J. Chem. Soc., Dalton Trans., 1998, 255
DOI: 10.1039/A707422K

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