周锡庚
金属有机化学、基于稀土金属参与的新有机合成方法学和配位化学。
个性化签名
- 姓名:周锡庚
- 目前身份:
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学术头衔:
博士生导师, 优秀教师/优秀教育工作者, 教育部“新世纪优秀人才支持计划”入选者
- 职称:-
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学科领域:
有机化学
- 研究兴趣:金属有机化学、基于稀土金属参与的新有机合成方法学和配位化学。
周锡庚 (Xigeng Zhou), 复旦大学化学系教授,博士生导师。男,1963年10月10日生。1986年毕业于华中师范大学化学系获理学学士学位,1989年7月在安徽师范大学获硕士学位,1996年7月获南京大学理学博士学位。1989年7月-1996年7月在安徽师范大学有机所工作,1995年晋升为副教授,1996年8月入复旦大学化学博士后流动站工作,1998年5月出站留化学系工作, 2000年晋升为教授、博士生导师。主要研究方向为:金属有机化学、基于稀土金属参与的新有机合成方法学和配位化学。迄今共主持了近20项国家及省市部门科学基金或研究开发课题,发现了10余种重要的稀土金属有机新反应,如Me2SiO插入金属-氮键反应、羰基诱导的稀土金属有机化合物对芳环共轭加成反应、氧插入稀土-硫键反应等。在国内外核心期刊上发表研究论文80余篇。这些论文已被同行在《Chem. Rev.》; 《J. Am. Chem. Soc.》; 《Angew. Chem. Int. Ed. Engl.》等重要学术期刊上共引用300余次。获国家教委科技进步二等奖2项,安徽省教委科技进步一等奖1项。曾获上海市“曙光学者”、教育部“优秀青年教师”、教育部“跨世纪优秀人才”等称号。
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周锡庚, Xi-geng Zhou, * Li-bei Zhang, Ming Zhu, Rui-fang Cai, and Lin-hong Weng Zi-xiang Huang and Qiang-jin Wu
Organometallics 2001, 20, 5700-5706,-0001,():
-1年11月30日
Cp`2LnR(THF) (Cp`=C5H4CH3) reacted with phenyl isocyanate to form the PhNCO insertion products [Cp
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周锡庚, Jie Zhang, †, Ruyi Ruan, Zehuai Shao, Ruifang Cai, Linhong Weng, † and Xigeng Zhou*, ‡
Organometallics 2002, 21, 1420-1424,-0001,():
-1年11月30日
The synthesis, structures, and reactivity of new lanthanocene complexes incorporating amidinate ligand [tBuN.C(nBu).NtBu] are described. Treatment of Cp2LnnBu (Ln) Er (1), Y (2), Gd (3)) with N,N
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周锡庚, Xi-geng Zhou, Zu-en Huang, * Rui-fang Cai, Li-bei Zhang, and Li-xin Zhang Xiao-ying Huang
Organometallics 1999, 18, 4128-4133,-0001,():
-1年11月30日
Reactions of Cp3Ln (Cp) C5H5; Ln) Ho, Dy, Yb, Sm) with 2 equiv of HPzMe2 (HPzMe2=3,5-dimethylpyrazole) in THF at room temperature yield complexes CpLn(PzMe2)2 [Ln=Ho (1), Dy (2)], Cp2Yb(PzMe2)(HPzMe2) (3), and Sm(PzMe2)3 (5), respectively, indicating that the number of cyclopentadienyl groups liberated from a Cp3Ln moiety is largely influenced by the size of the lanthanide ion. Reaction of Cp3Er and 1 equiv of HPzMe2 under the same conditions gave Cp2Er(PzMe2)(THF) (4). The structures of 3 and 4 were determined by X-ray diffraction. In both complexes the central metal ions are coordinated to four ligands in a typical "bent metallocene" geometry. Complexes 1 and 2 react with dimethylsilicone grease to give the corresponding Me2SiO insertion products [CpLn(PzMe2)(OSiMe2PzMe2)]2 [Ln=Ho (6), Dy (7)]. The results of the investigation show that the insertion of dimethylsilicone into the Ln-N bond is only possible for the monocyclopentadienyl-type organolanthanide pyrazolates. X-ray diffraction reveals complex 6 to be a centrosymmetric dimer in which each holmium atom is coordinated to one cyclopentadienyl group, two bridging oxygen atoms, and three nitrogen atoms, two from the chelating PzMe2 ligand and one from the bridging 3,5-dimethylpyrazolyl siloxide ligand to form a distorted octahedron.
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【期刊论文】Insertion of a Carbodiimide into the Ln-N
周锡庚, Jie Zhang, † Ruifang Cai, † Linhong Weng, † and Xigeng Zhou*, †, ‡
Organometallics 2004, 23, 3303-3308,-0001,():
-1年11月30日
The reaction of (C5H5)YCl2(THF)3 with LiNiPr2 and subsequently with 2 equiv of N,N
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周锡庚, Chunmei Zhang, †, Ruiting Liu, Xigeng Zhou, *, ‡, Zhenxia Chen, Linhong Weng, † and Yanghui Lin†
Organometallics 2004, 23, 3246-3251,-0001,():
-1年11月30日
Treatment of [Cp2Ln(μ-SEt)]2 with PhRCdCdO gives dimeric complexes [Cp2Ln(μ-η1:η2-OC(SEt)dCPhR)]2 [R=Ph, Ln=Yb (1), Er (2), Sm (3), Y (4); R=Et, Ln=Er (5)], which represent the first example of ketene insertion into a metal-sulfur bond and provide an efficient method for the synthesis of organolanthanides with a β-thiolate-substituted enolate ligand. It is found that an excess of ketene does not affect the nature of the final complexes, with only a single insertion being observed. All these complexes are characterized by elemental analysis and spectroscopic properties. The structures of complexes 1âC6H5CH3, 2•C6H5CH3, and 5âTHF are determined through single-crystal X-ray diffraction analysis.
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周锡庚, Jie Zhang, †, Ruifang Cai, Linhong Weng, † and Xigeng Zhou*, ‡
Organometallics 2003, 22, 5385-5391,-0001,():
-1年11月30日
Two ytterbocene derivatives containing aromatic nitrogen ligands, (C5H5)2YbCbz(THF) (1) and (C5H5)2YbPzMe2(THF) (4), were synthesized, and their reactivities toward N,N¢- diisopropylcarbodiimide, phenyl isothiocyanate, and phenyl isocyanate were studied. Abstraction of cyclopentadienyl from (C5H5)3Yb with 1 equiv of carbazole (HCbz) in THF at room temperature gives 1. Reaction of 1 with N,N¢-diisopropylcarbodiimide (iPrN=C=NiPr) results in monoinsertion of iPrN=C=NiPr into the Yb-N(Carbazolate) bond, yielding the ytterbocene guanidinate (C5H5)2Yb[iPrN−C(Cbz)−NiPr] (2), while treatment of 1 with 1 equiv of phenyl isothiocyanate (PhNCS) gives the unexpected monocyclopentadienylytterbium complex (C5H5)Yb[S−C(Cbz) −NPh]2(THF) (3) and (C5H5)3Yb(THF), which may be rationalized by the ligand rearrangement of the monoinsertion product (C5H5)2Yb[S−C(Cbz)−NPh]. (C5H5)3-Yb reacts with 3,5-dimethylpyrazole (HPzMe2) in a 1:1 ratio at ambient temperature to form complex 4. Reaction of 4 with PhNCO gives the insertion product (C5H5)2Yb[OC(=NPh)- PzMe2](THF) (5). In contrast to 1, however, complex 4 does not react with iPrNCNiPr under the same conditions. All these complexes were characterized by elemental analysis and spectroscopic properties. The structures of complexes 2-5 were also determined by X-ray single-crystal diffraction analyses. These reactions present the first example of 1,3- heterocumulene insertions into the Ln-N(aromatic ring) bond and provide a new strategy for introducing a substituent at the nitrogen atom of organic heterocycle compounds.
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【期刊论文】Insertions into lanthanide ligand bonds in organolanthanide chemistry
周锡庚, Xigeng Zhou a, b, *, Ming Zhu a
Journal of Organometallic Chemistry 647(2002)28-49,-0001,():
-1年11月30日
Insertions of small molecules into lanthanide-ligand bonds have led to a number of new organolanthanide derivatives. Many attractive catalytic transformations are also based on these insertion reactions. The focus of this review concerns these important stoichiometric and catalytic transformations.
Insertion, Catalysis, Organolanthanide, Review
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周锡庚, Jie Zhang a, Ruifang Cai a, Linhong Weng a, Xigeng Zhou a, b, *
Journal of Organometallic Chemistry 672(2003)94-99,-0001,():
-1年11月30日
The synthesis and structures of three new lanthanide complexes incorporating tetra-substituted guanidinate ligand [iPrN-C(NiPr2)-/Ni Pr] are described. Treatment of Cp2LnNiPr2(-THF) (Ln=/Yb, Dy, Gd) with N,N'-di-isopropyl-carbodiimide results in mono-insertion of carbodiimide into the Ln-N σ-bond to yield Cp2Ln[iPrN-C(NiPr2)-Ni Pr] (Ln=Yb(1), Dy(2), Gd(3), providing an efficient method for the synthesis of organolanthanide guanidinate complexes. It was found that an excess of N, N'-diisopropyl-carbodiimide did not affect the nature of the final product. Complexes 1=3 were characterized by elemental analysis, IR and mass spectroscopies. Complexes 1 and 2 were determined by the X-ray single crystal diffraction analysis.
Organolanthanide, Insertion, Carbodiimide, Structures, Cyclopentadienyl
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周锡庚, Jun Luo a, Xi-Geng Zhou a, *, Song Gao b, Lin-Hong Weng a, Ze-Huai Shao a, Chun-Mei Zhang a, Yan-Rong Li a, Jie Zhang a, Rui-Fang Cai a
Inorganic Chemistry Communications 7(2004)669-672,-0001,():
-1年11月30日
Two isomorphous novel 3D helical dicyanamide complexes, Co(tmeda)(dca)2 (1) and Ni(tmeda)(dca)2 (2) (tmeda¼tetramethylethylenediamine) have been synthesized and their crystal structures, IR spectra, magnetic properties were determined. Complex 1 displays antiferromagnetic coupling (T >70K, h=-27 K, C=3:78 cm3 mol-1 K) between the adjacent cobalt(II) ions, while weak ferromagnetic interaction (θ=3.8 K, C=1.12 cm3 mol-1 K) is observed in complex 2.
Dicyanamide, 3D helical complexes, Coordination polymers, Polyamine, Crystal structures, Magnetic properties
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周锡庚, Ruyi Ruan, a, Jie Zhang, Xigeng Zhou*a, b and Ruifang Cai*a
,-0001,():
-1年11月30日
In the presence of Cp2LnX-HgCl2, the treatment of RC
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