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Titanium Imido Complexes of Cyclooctatetraenyl Ligands

  1. Simon C. Dunn Dr.1,
  2. Nilay Hazari1,
  3. Nicholas M. Jones1,
  4. Aidan G. Moody Dr.1,
  5. Alexander J. Blake Dr.2,
  6. Andrew R. Cowley Dr.1,
  7. Jennifer C. Green Prof.1,
  8. Philip Mountford Dr.1

Article first published online: 15 FEB 2005

DOI: 10.1002/chem.200401104

Issue

Chemistry - A European Journal

Chemistry - A European Journal

Volume 11, Issue 7, pages 2111–2124, March 18, 2005

Additional Information

How to Cite

Dunn, S. C., Hazari, N., Jones, N. M., Moody, A. G., Blake, A. J., Cowley, A. R., Green, J. C. and Mountford, P. (2005), Titanium Imido Complexes of Cyclooctatetraenyl Ligands. Chem. Eur. J., 11: 2111–2124. doi: 10.1002/chem.200401104

Author Information

  1. 1

    Inorganic Chemistry Laboratory, University of Oxford, South Parks Road, Oxford OX1 3QR, UK, Fax: (+44) 1865-285-141

  2. 2

    Department of Chemistry, University of Nottingham, Nottingham NG7 2RD, UK

Publication History

  1. Issue published online: 9 MAR 2005
  2. Article first published online: 15 FEB 2005
  3. Manuscript Received: 2 NOV 2004

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Keywords:

  • cyclooctatetraenyl ligands;
  • density functional calculations;
  • imido compounds;
  • photoelectron spectroscopy;
  • titanium

Abstract

Reaction of [Ti(NR)Cl2(py)3] (R=tBu or 2,6-iPr2C6H3) with K2[COT] (COT=C8H8) or Li2[COT′′] (COT′′=1,4-C8H6(SiMe3)2) gave the monomeric complexes [Ti(NR)(η8-COT)] or [Ti(NR)(η8-COT′′)], respectively. The pseudo-two coordinate, ′pogo stick′ geometry for these complexes is unique in both early transition-metal and cyclooctatetraenyl ligand chemistry. In contrast, reaction of [Ti(N-2,6-Me2C6H3)Cl2(py)3] with K2[COT] gave the μ-imido-bridged dimer [Ti2(μ-N-2,6-Me2C6H3)2(η8-COT)2]. It appears that as the steric bulk of the imido and C8 ring substituents are decreased, dimerisation becomes more favourable. Aryl imido COT complexes were also prepared by imido ligand exchange reactions between anilines and [Ti(NtBu)(η8-COT)] or [Ti(NtBu)(η8-COT′′)]. The complexes [Ti(NtBu)(η8-COT)], [Ti(N-2,6-iPr2C6H3)2(η8-COT)] and [Ti2(μ-N-2,6-Me2C6H3)2(η8-COT)2] have been crystallographically characterised. The electronic structures of both the monomeric and dimeric complexes have been investigated by using density functional theory (DFT) calculations and gas-phase photoelectron spectroscopy. The most striking aspect of the bonding is that binding to the imido nitrogen atom is primarily through σ and π interactions, whereas that to the COT or COT′′ ring is almost exclusively through δ symmetry orbitals. A DFT-based comparison between the bonding in [Ti(NtBu)(η8-COT)] and the bonding in the previously reported late transition-metal ′pogo-stick′ complexes [Os(NtBu)(η6-C6Me6)], [Ir(NtBu)(η5-C5Me5)] and [Ni(NO)(η5-C5H5)] has also been undertaken.

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