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

doi:10.1021/ic049474f

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 journal › Article › peer-review

42 Scopus citations

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 language	English (US)
Pages (from-to)	6786-6792
Number of pages	7
Journal	Inorganic Chemistry
Volume	43
Issue number	21
DOIs	https://doi.org/10.1021/ic049474f
State	Published - Oct 18 2004
Externally published	Yes

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

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@article{dc21569631b041f0ad79be3ff667ea89,

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

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.",

author = "Hsu, {Shih Hsien} and Chang, {Jr Chiuan} and Lai, {Chun Liang} and Hu, {Ching Han} and Lee, {Hon Man} and Lee, {Gene Hsiang} and Peng, {Shie Ming} and Huang, {Jui Hsien}",

year = "2004",

month = oct,

day = "18",

doi = "10.1021/ic049474f",

language = "English (US)",

volume = "43",

pages = "6786--6792",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "21",

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TY - JOUR

T1 - Terminal titanium-ligand multiple bonds. Cleavages of C=O and C=S double bonds with Ti imido complexes

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

Y1 - 2004/10/18

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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U2 - 10.1021/ic049474f

DO - 10.1021/ic049474f

M3 - Article

C2 - 15476379

AN - SCOPUS:6344219660

SN - 0020-1669

VL - 43

SP - 6786

EP - 6792

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 21

ER -

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

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