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徐善生, Gonglu Tiana, Baiquan Wanga, *, Xuliang Daia, Shansheng Xua, Xiuzhong Zhoua, Jie Sunb
Journal of Organometallic Chemistry 634(2001)145-152,-0001,():
-1年11月30日
The ansa-metallocene complexes Me2Si(η5-C5H4)(η5-C5Me4)MEI2[M=Ti(1),Zr(2),Hf(3)] were prepared by the reaction of [Me2Si(η5-C5H4)(η5-C5Me4)]Li2 with MCI4 2THF. Complexes Me2Ge(η5-C5H4)(η5-C5Me4)MCI2[M=Ti(4),Zr (5)]were synthe-sized using similar method from the germyl-bridged ligand. The molecular structures of 1-3 and 5 have been determinde by X-ray diffraction. Complexes 1-3 and 5 in combination with MAO were studied as catalysts for ethylene polymerization and it was found that zirconocene catalysts show much higher activities than the titanocene and hafnocene and the activities reach the maximum at high temperature. This indicates that the zirconocene system based upon [Me2E(C5H5)(C5Me4)]2 (E=Si, Ge) supporting coordination is a highly stable ethylene polymerization catalyst system. The relationship between structures and catalytic properties of catalysts is discussed.
Titanocene, Zirconocene, Metallocne, Polymerization
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徐善生, Shansheng Xu, Xuliang Dai, Baiquan Wang*, Xiuzhong, Zhou
Journal of Organometallic Chemistry 645(2002)262-267,-0001,():
-1年11月30日
The ansa-metallocene complexes Me2Ge(η5-C5Me4)2MCI2[M=Ti(1), Zr(2)], Me2Ge(η5-C5H3Bu-t)2ZrCl2(3) and Me2Ge(η5-C5H4)(η5-C5H3R)ZrCl2[R=Me(4), t-Bu (5)] were prepared by the reaction of the corresponding ligands with n-BuLi and MCl4 2THF, respectively. The molecular structures of 1 and 2 have benn determinde by the X-ray diffraction method. Complexe 2-5 in combination with MAO were studied as catalysts for ethylene polymerizatiion and all the germyl-bridged zirconocene catalysts show high activities at relative high temperatures. This indicates that the germyl-bridged zirconocene systems show thermally stable catalyst sysstems for polymerization of ethylene.
Titanocene, Zirconocene, Metallocne, Polymerization
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徐善生, Shansheng Xu, Xuliang Dai, Tao Wu, Baiquan Wang*, Xiuzhong, Zhou, Linhong Weng
Journal of Organometallic Chemistry 645(2002)212-217,-0001,():
-1年11月30日
A series of doubly bridged dinuclear titanium and zirconium complexes (Me2C)(Me2E)(C5H3)2(Cp'MCI2)2 [E=Si,Cp'=C5H5, M=Ti (1), Zr (2); E=Ge, Cp'=C5H5, M=Ti (3), Zr (4); Cp'=C5Me4H, M=Zr, E=Si (5), Ge (6)] and (Me2SiOSiMe2)2(C5H3)2(Cp'MCI2)2[Cp'=C5H5, M=Ti (7), Zr (8); Cp=C5Me4H, M=Zr (9)] were synthesized by the reaction of the lithium compounds of the corresponding doubly bridged cyclopentadienyl ligands with CpTiCl3, CpZrCl3(THF)2 or C5Me4HZrCl3, respectively. These complexes were characterized by 1H-NMR, MS and elemental analysis. The crystal structure of 4 was determined by the X-ray diffraction. Their catalytic properties for ethylene polymerization were also studied in the presence of MAO.
Titanium, Zirconium, Doubly bridged, Dinuclear, Polymerization
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徐善生, Yongqiang Zhang, Baiquan Wang, * Shansheng XU, and Xiuzhong Zhou
Organometallics 2001, 20, 3829-3832,-0001,():
-1年11月30日
A novel trigonal-bipyramidal ruthenium car-bonyl cluster, [(μ3-Ge){Ru(CO)2(η5-C5Me4H)}]2Ru3(CO)9(3), was accidentally synthesized by thermal treatment of Ru3(CO)12 and C5Me4HMe2GeGeMe2C5Me4H in boil-ing decalin, along with the dinuclear ruthenium complex [(Me2Ge)(η5-C5Me4)Ru2(CO6] (4). Similar treatment of Ru3(CO)12 and C5H5Me2GeGeMe2C5H5 in boiling hep-tane afforded three different bimetallic complexes, [(Me2-Ge)(η5-C5H4)Ru2(CO)6] (1), [(Me2Ge)(η5-C5H4)Ru(CO)2]2 (2), and dimer [(η5-C5H5)Ru(CO)2]2. Molecular structures of 2,3, and 4 have benn determined by single-crystal X-ray diffraction.
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徐善生, Baiquan Wang, Yongqiang Zhang, Shansheng Xu, and Xiuzhong Zhou*
Organometallics 1997, 16, 4620-4625,-0001,():
-1年11月30日
The catalytic hydrogenation of the indenyl complex(Me2SiSiMe2)[η5-Ind)Fe(CO)]2(μ-CO)2(2) in CH2Cl2 afforded the tetrahyroindenyl complex (Me2SiSiMe2)[(η5-IndH4)Fe(CO)]2(μ-CO)2 (3), existing as a mixture of cis and trans isomers (3c and 3t), which were separated by column chromatography. When the two isomers were heated in xylene, respectively, the cis substrate 3c rearranged to the trans product [Me2Si(η5-IndH4)Fe(CO)2]2 (4c). This indicates that the rearrangement reaction is stereospecific, which is consistent with the result observed in the rearrangement of complex(Me2SiSiMe2)[η5-t-BuC5H3)Fe(CO)]2(μ-CO)2(5). By analogy with the mechanism porposed based on detailed investigation of 5, the pathway for formation of 4 is described. Molecular structures of 3c, 3t, 4t, and 4c were determinde by X-ray diffraction.
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