کد مقاله | کد نشریه | سال انتشار | مقاله انگلیسی | نسخه تمام متن |
---|---|---|---|---|
5190637 | 1381213 | 2006 | 13 صفحه PDF | دانلود رایگان |
عنوان انگلیسی مقاله ISI
Syntheses of group 4 transition metal complexes bearing 2-pyridinethiolate ligands and their catalytic activities for ethylene polymerization
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موضوعات مرتبط
مهندسی و علوم پایه
شیمی
شیمی آلی
پیش نمایش صفحه اول مقاله

چکیده انگلیسی
Titanium bis(2-pyridinethiolate) complexes, Ti(6-R-SPy)2(NMe2)2 (6-R-SPy = 6-R-2-pyridinethiolate, 3a: R = H; 3b: R = Me; 3c: R = Ph; 3d: R = C6H4-4-Me; 3e: R = C6H4-4-t-Bu; 3f: R = C6H3-3,5-Me2), and the titanium bis(2-pyridinolate) complexes, Ti(6-Ph-OPy)2(NMe2)2 (6-Ph-OPy = 6-phenyl-2-pyridinolate, 8) were prepared by treating Ti(NMe2)4 with 2 equiv. of 6-R-2-pyridinethiol or 6-Ph-2-pyridinol. The cis-configuration of the diamido moieties in the pseudo octahedral geometry was elucidated by X-ray crystallography for 3a. Reaction of M(NMe2)4 (M = Ti, Zr) with 4 equiv. of 2-pyridinethiol cleanly gave tetrakis(pyridinethiolate) complexes, M(6-H-SPy)4·THF (6: M = Ti; 7: M = Zr). The triangular dodecahedral geometries of 6 and 7 were also revealed by X-ray crystallography. These complexes catalyzed ethylene polymerization upon activation with MAO (methylaluminoxane) or MMAO (modified MAO). The catalytic activities of titanium bis(6-aryl-pyridinethiolate) systems were found to be remarkably higher than that of titanium bis(6-methyl-pyridinethiolate) system. Among the complexes synthesized in this study, Ti[6-(C6H3-3,5-Me2)-SPy]2(NMe2)2 (3f)/MMAO showed the highest activity (1200 kg/Ti-mol h atm) for ethylene polymerization at 60 °C under atmospheric pressure. In contrast, the activity of the corresponding 6-aryl-pyridinolate system 8/MMAO was rather low (9.3 kg/Ti-mol h atm). Both the N-S chelating structure and the bulky aryl substituents are essential for the high activities of the 6-aryl-pyridinethiolate complexes.
ناشر
Database: Elsevier - ScienceDirect (ساینس دایرکت)
Journal: Polymer - Volume 47, Issue 16, 26 July 2006, Pages 5762-5774
Journal: Polymer - Volume 47, Issue 16, 26 July 2006, Pages 5762-5774
نویسندگان
Yoshinori Takashima, Yuushou Nakayama, Mika Hashiguchi, Takashi Hosoda, Hajime Yasuda, Toshikazu Hirao, Akira Harada,