Terminal titanium-ligand multiple bonds. Cleavages of C=O and C=S double bonds with Ti imido complexes

Shih Hsien Hsu, Jr Chiuan Chang, Chun Liang Lai, Ching Han Hu, Hon Man Lee, Gene Hsiang Lee, Shie Ming Peng, Jui Hsien Huang

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47 Scopus citations


Treatment of t-BuN=TiCl2Py3 with 2 equiv lithium ketiminate compound, Li[OCMeCHCMeN(Ar)] (where Ar = 2,6- diisopropylphenyl), in toluene at room temperature gave t-BuN= Ti[OCMeCHCMeN(Ar)]2 (1) in high yield. The reaction of 1 with phenyl isocyanate at room-temperature resulted in imido ligand exchange producing PhN=Ti[OCMeCHCMeN(Ar)]2 (2). Compound 1 decomposed at 90 °C to form a terminal titanium oxo compound O=Ti[OCMeCHCMeN(Ar)]2 (3) and t-BuNHCMeCHCMeNAr (4). Also, the compound 3 could be obtained by reacting 1 with CO2 under mild condition. Similarly, while 1 reacts with an excess of carbon disulfide, a novel terminal titanium sulfido compound S=Ti[OCMeCHCMeN(Ar)]2 (5) was formed via a C=S bond breaking reaction. A novel titanium isocyanate compound Ti[OCMeCHCMeN(Ar)] 2(NCO)(OEt) (6) was formed on heating 1 with 1 equiv of urethane, H2NCOOEt. Compounds 1-6 have been characterized by 1H and 13C NMR spectroscopies. The molecular structures of 1, 3, 5, and 6 were determined by single-crystal X-ray diffraction. A theoretical calculation predicted that the cleavage of the C-S double bonds for carbon disulfide with the Ti=N bond of compound 1 was estimated at ca. 21.8 kcal·-mol -1 exothermic.

Original languageEnglish (US)
Pages (from-to)6786-6792
Number of pages7
JournalInorganic Chemistry
Issue number21
StatePublished - Oct 18 2004
Externally publishedYes

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry


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