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

Research output: Contribution to journalArticle

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Abstract

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
Volume43
Issue number21
DOIs
StatePublished - Oct 18 2004
Externally publishedYes

Fingerprint

Titanium compounds
titanium compounds
Carbon Disulfide
carbon disulfide
isocyanates
Titanium
cleavage
Lithium Compounds
titanium
lithium compounds
Ligands
Isocyanates
urethanes
ligands
Urethane
Toluene
room temperature
Molecular structure
Nuclear magnetic resonance spectroscopy
toluene

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Hsu, S. H., Chang, J. C., Lai, C. L., Hu, C. H., Lee, H. M., Lee, G. H., ... Huang, J. H. (2004). Terminal titanium-ligand multiple bonds. Cleavages of C=O and C=S double bonds with Ti imido complexes. Inorganic Chemistry, 43(21), 6786-6792. https://doi.org/10.1021/ic049474f

Terminal titanium-ligand multiple bonds. Cleavages of C=O and C=S double bonds with Ti imido complexes. / Hsu, Shih Hsien; Chang, Jr Chiuan; Lai, Chun Liang; Hu, Ching Han; Lee, Hon Man; Lee, Gene Hsiang; Peng, Shie Ming; Huang, Jui Hsien.

In: Inorganic Chemistry, Vol. 43, No. 21, 18.10.2004, p. 6786-6792.

Research output: Contribution to journalArticle

Hsu, SH, Chang, JC, Lai, CL, Hu, CH, Lee, HM, Lee, GH, Peng, SM & Huang, JH 2004, 'Terminal titanium-ligand multiple bonds. Cleavages of C=O and C=S double bonds with Ti imido complexes', Inorganic Chemistry, vol. 43, no. 21, pp. 6786-6792. https://doi.org/10.1021/ic049474f
Hsu, Shih Hsien ; Chang, Jr Chiuan ; Lai, Chun Liang ; Hu, Ching Han ; Lee, Hon Man ; Lee, Gene Hsiang ; Peng, Shie Ming ; Huang, Jui Hsien. / Terminal titanium-ligand multiple bonds. Cleavages of C=O and C=S double bonds with Ti imido complexes. In: Inorganic Chemistry. 2004 ; Vol. 43, No. 21. pp. 6786-6792.
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abstract = "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.",
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AU - Hsu, Shih Hsien

AU - Chang, Jr Chiuan

AU - Lai, Chun Liang

AU - Hu, Ching Han

AU - Lee, Hon Man

AU - Lee, Gene Hsiang

AU - Peng, Shie Ming

AU - Huang, Jui Hsien

PY - 2004/10/18

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N2 - 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.

AB - 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.

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