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http://ir.ncue.edu.tw/ir/handle/987654321/10076
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| Title: | Terminal Titanium-Ligand Multiple Bonds. Cleavages of C＝O and C＝S Double Bonds with Ti Imido Complexes |
| Authors: | Hsu, S. H.;Chang, J. C.;Lai, C. L.;Hu, Ching-Han;Lee, H. M.;Lee, G. H.;Peng, S. M.;Huang, J. H. |
| Contributors: | 化學系 |
| Date: | 2004-10
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| Issue Date: | 2012-05-03T06:17:48Z
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| Publisher: | American Chemical Society |
| Abstract: | 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. |
| Relation: | Inorg. Chem., 43(21): 6786-6792 |
| Appears in Collections: | [化學系] 期刊論文
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