Density functional theory calculations of Ti - TEMPO complexes: Influence of ancillary ligation on the strength of the Ti - O bond

Kuo Wei Huang, Joseph H. Han, Charles B. Musgrave*, Robert M. Waymouth

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

16 Scopus citations

Abstract

A series of mono(cyclopentadienyl)titanium TEMPO (2,2,6,6- tetramethylpiperidine-N-oxyl) complexes were investigated by density functional theory (DFT) calculations to study the influence of the ligands on the Ti - O bond energies. Mono-Cp complexes with pendant amino groups were found to possess significantly weaker Ti - O bonds than those lacking pendant donor ligands. On the basis of DFT predictions, a novel mono-Cp pendant dimethylamino complex, Cp NTiCl 2(TEMPO) (12; Cp N = C 5H 4CH 2CH 2N(CH 3) 2), was identified as a mono-Cp titanium TEMPO complex with a weak Ti - O bond (25 kcal/mol). The calculated bond energy of this complex is comparable to that of Cp 2TiCl(TEMPO) (3; 17 kcal/mol). Thermolysis of 12 in the presence of CC1 4 at 100 °C resulted in the formation of Cp NTiCl 3, consistent with the predicted low Ti - O bond energy.

Original languageEnglish (US)
Pages (from-to)3317-3323
Number of pages7
JournalOrganometallics
Volume25
Issue number14
DOIs
StatePublished - Jul 3 2006
Externally publishedYes

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry

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