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Synthesis of new adducts and co-ordination complexes of zirconium and titanium containing beta-aminoketone ligands. Crystal structures of isostructural adducts MCl4·2Pr(i)HNCMe=CHCMe=O (M = Ti or Zr) and the complex [Zr(PhNCMe=CHCMe=O)(2)Cl-2]

Citation

Jones, DJ and Roberts, AS and Cavell, KJ and Keim, K and Englert, U and Skelton, BW and White, AH, Synthesis of new adducts and co-ordination complexes of zirconium and titanium containing beta-aminoketone ligands. Crystal structures of isostructural adducts MCl4·2Pr(i)HNCMe=CHCMe=O (M = Ti or Zr) and the complex [Zr(PhNCMe=CHCMe=O)(2)Cl-2], Journal of the Chemical Society, Dalton Transactions, (2) pp. 255-262. ISSN 0300-9246 (1998) [Refereed Article]

DOI: doi:10.1039/a707422k

Abstract

The reaction of MCl 4 (M = Zr or Ti) with β-aminoketones HL (R 1 HNCR 2 =CHCR 3 =O; R 2 = R 3 = Me; R 2 = Me, R 3 = CF 3 ) yielded the bis(ligand) adducts MCl 4 ·2HL (M = Zr, R 1 = Pr i or Ph; R 2 = R 3 = Me; or R 1 = Pr i , R 2 = Me, R 3 = CF 3 ; M = Ti, R 1 = Pr i or CH 2 CH=CH 2 , R 2 = R 3 = Me). Reaction of MCl 4 with the alkali-metal salts of the β-aminoketone ligands yielded the bis(ligand) complexes [M(R 1 NCMe=CHCMe=O) 2 Cl 2 ] (M = Zr, R 1 = Ph, p-ClC 6 H 4 , p-MeOC 6 H 4 or Pr i ; M = Ti, R 1 = Ph or p-MeOC 6 H 4 ). Crystal structure determinations of the isostructural compounds ZrCl 4 ·2Pr i HNCMe=CHCMe=O and TiCl 4 ·2Pr i HNCMe=CHCMe=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=CHCMe=O) 2 Cl 2 ] 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.

Item Details

Item Type:Refereed Article
Research Division:Chemical Sciences
Research Group:Inorganic Chemistry
Research Field:Transition Metal Chemistry
Objective Division:Expanding Knowledge
Objective Group:Expanding Knowledge
Objective Field:Expanding Knowledge in the Chemical Sciences
Author:Jones, DJ (Dr Jones)
Author:Roberts, AS (Dr Andrew Roberts)
Author:Cavell, KJ (Professor Kingsley Cavell)
ID Code:14124
Year Published:1998
Web of Science® Times Cited:49
Deposited By:Chemistry
Deposited On:1998-08-01
Last Modified:2011-08-09
Downloads:0

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