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題名: Terminal Titanium-Ligand Multiple Bonds. Cleavages of C=O and C=S Double Bonds with Ti Imido Complexes
作者: Hsu, Shih-Hsien;Chang, Jr-Chiuan;Lai, Chun-Liang;Hu, Ching-Han;Lee, Hon-Man;Lee, Gene-Hsiang;Peng, Shie-Ming;Huang, Jui-Hsien
貢獻者: 化學系
日期: 2004
上傳時間: 2012-12-10T01:39:34Z
出版者: American Chemical Society
摘要: Treatment of t-BuNTiCl2Py3 with 2 equiv lithium ketiminate compound, Li[OCMeCHCMeN(Ar)] (where Ar = 2,6-diisopropylphenyl), in toluene at room temperature gave t-BuNTi[OCMeCHCMeN(Ar)]2 (1) in high yield. The reaction of 1 with phenyl isocyanate at room-temperature resulted in imido ligand exchange producing PhNTi[OCMeCHCMeN(Ar)]2 (2). Compound 1 decomposed at 90 °C to form a terminal titanium oxo compound OTi[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 STi[OCMeCHCMeN(Ar)]2 (5) was formed via a CS 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 TiN bond of compound 1 was estimated at ca. 21.8 kcal·mol-1 exothermic.
關聯: Inorg. Chem., 43(21): 6786-6792
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