王绍武
稀土金属有机化学方面
个性化签名
- 姓名:王绍武
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- 担任导师情况:
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学术头衔:
博士生导师, 教育部“新世纪优秀人才支持计划”入选者
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学科领域:
有机化学
- 研究兴趣:稀土金属有机化学方面
王绍武,博士,1964年1月生于安徽六安。长期从事有机化学、金属有机化学的教学、研究与人才培养工作。现任安徽师范大学博士生导师,安徽省“皖江学者”特聘教授,化学与材料科学学院院长,有机化学省级重点学科、有机化学博士点学科负责人,安徽省学术与技术带头人后备人选。2004年入选教育部“新世纪优秀人才”支持计划,2006年入选“新世纪百千万人才工程”国家级人选。在稀土金属有机化学方面的研究具有特色和创见,取得了一系列有意义的研究成果,先后在国际性学术刊物上发表学术论文50多篇,其中在国际性重要杂志Organometallics, J. Org. Chem.; Org. Lett.; J. Chem. Soc.; Chem. Commun.上发表学术论文20多篇。近期首次发现一个新型稀土金属-氮键均裂反应,该反应为稀土金属-氮键共价性特征提供了实验证据,并发展了一种合成二价稀土金属有机络合物的新方法,发展了多个单一组分极性单体聚合反应催化剂,已申报中国专利两项,获授权专利1项。研究成果受到国内外同行的广泛关注。学术论文被同行引用100多次。近年先后受邀在国际性学术会议上作邀请报告1次,分组学术报告3次,全国性学术会议上作学术报告4次,其中邀请报告1次。并受邀撰写《稀土金属有机化学》学术专著第八章(2004年出版)。先后获国家教委科技进步二等奖一项(1996年),安徽省自然科学二等奖一项(2000年),安徽省高等学校科技进步一等奖一项(1999年)。2001年起任中科院上海有机所金属有机化学国家重点实验室客座教授,2002年5月起任中国科技大学兼职博士生导师。近4年来,主持国家自然科学基金项目4项(在研项目两项),安徽省优秀青年基金项目2次(其中1次滚动支持),及其它省部级基金项目多项项。近3年先后培养毕业博士研究生1名,硕士研究生15名,正在培养博士生4名,硕士研究生10名。
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503
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成果数
14
王绍武, Xiang Fang, a, b, Yong-Ming Wu, *, Juan Denga, and Shao-Wu Wangb
Tetrahedron 60 (2004) 5487-5493,-0001,():
-1年11月30日
Monofluorinated indolizines 4, benzo[d]indolizines 7 and 4H-pyrrolo[1,2-a]benzimidazoles 8 were synthesized in moderate yields by 1,3-dipolar reaction between fluorinated vinyl tosylates 2a and N-ylides of pyridinium, isoquinolinium and benzimidazolinium, generated in situ from their halides salts. When the same N-ylides were allowed to react with 2,3,3-trifluoro-1-propenyl tosylate 2b, the unexpected product formylated indolizines and their derivatives 9 were obtained. The reaction mechanism is also proposed.
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王绍武, Shaowu Wang, a, b, Yaorong Wang, Mak-Shuen Cheung, Hoi-Shan Chana, and Zuowei Xiea, *
Tetrahedron 59 (2003) 10373-10380,-0001,():
-1年11月30日
Several new 13-vertex closo-metallacarboranes of rare earths incorporating nido-and arachno-carborane ligands have been prepared and structurally characterized. They represent a new class of metallacarboranes bearing a h7-carboranyl ligand recently discovered in our laboratory. This work indicates that the substituents on carborane cage carbons may affect the overall molecular structures of the resultant 13-vertex closo-metallacarborane complexes, but have little influence on the interactions between the central metal ion and nido- or arachno-carborane ligand.
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王绍武, Xins yuan Liu, a, b, Shizheng Zhu, *b, Shaowu Wang*a
SYNTHESIS 2004, No.5, pp 0683-0691,-0001,():
-1年11月30日
The intermolecular additions of alkyl halides to per-(or poly)fluorophenyl aromatic aldimines using zinc as a single-electron-transfer radical initiator have been studied in aqueous media. The reaction proceeds well for imines with different substituents at room temperature under air atmosphere and the corresponding fluorine-containing amines and 1,2-diamines are obtained in poor to good yields. A tentative reaction mechanism is proposed.
polyfluororinated amines,, imines,, zinc,, alkyl halides,, radical reactions
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王绍武, Shaowu Wang, Qingchuan Yang, Thomas C. W. Mak, and Zuowei Xie*
Organometallics 1999, 18, 4478-4487,-0001,():
-1年11月30日
A versatile compound, Me2Si(C9H7)(C2B10H11) can be conveniently converted into the monoanion [Me2Si(C9H6)(C2B10H11)]Na, the dianion [Me2Si(C9H6)(C2B10H10)]Na2, and the trianion [Me2Si(C9H6)(C2B10H11)]K3 by treatment with 1 equiv or excess amounts of NaH or K metal in THF, respectively. Reaction of LnCl3 with 1 equiv of [Me2Si(C9H6)(C2B10H11)]Na in THF gave dichloride complexes [η5-Me2Si(C9H6)(C2B10H11)]LnCl2(THF)3 (Ln) Nd (1), Er (2)). They can further react with another equivalent of [Me2Si(C9H6)(C2B10H11)]Na to afford monochloride complexes [η5-Me2Si(C9H6)(C2B10H11)]2LnCl(THF)2 (Ln) Ce (3), Nd (4), Sm (5), Er (6)), which can also be prepared by treatment of LnCl3 with 2 equiv of [Me2Si(C9H6)-(C2B10H11)]Na in THF. 4 reacts with excess NaH in THF to produce [Na(THF)6][{η5:σ-Me2-Si(C9H6)(C2B10H10)}2Nd] (7), which can also be prepared from the reaction of NdCl3 with 2 equiv of [Me2Si(C9H6)(C2B10H10)]Na2 in THF. Treatment of 2 with 2 equiv of K metal at room temperature yielded [η5:η6-Me2Si(C9H6)(C2B10H11)]Er(THF)2 (8). Reaction of 6 with 1 equiv of NaH afforded [{η5:σ-Me2Si(C9H6)(C2B10H10)}{η5-Me2Si(C9H6)(C2B10H11)}]Er(μ-Cl)-Na(THF)3 (9), which can also be prepared from the reaction of 2 with 1 equiv of [Me2Si-(C9H6)(C2B10H10)]Na2 in THF. Treatment of 9 with a mixture of 1 equiv of NaOH and excess NaH in THF generated the dinuclear complex [Na2(THF)11][{η5:σ-Me2Si(C9H6)(C2B10H10)}-{μ-η5:σ-(C9H6)SiMe2O}Er]2 (10). Treatment of Me2Si(C9H7)(C2B10H11) with excess NaH in THF under UV-light followed by reaction with 1 equiv of LnCl3 resulted in the isolation of unprecedented biscarborane compounds [LnCl2(THF)5][μ-CH-(closo-C2B10H11)-nido-CB10H11] (Ln) Er (11), Y (12)). All of these complexes were characterized by various spectroscopic and elemental analyses. The solid-state structures of 7 and 9-12 were confirmed by singlecrystal X-ray analyses.
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王绍武, Zuowei Xie, *, Shaowu Wang, Qingchuan Yang, and Thomas C. W. Mak
Organometallics 1999, 18, 2420-2427,-0001,():
-1年11月30日
Reaction of Me2Si(C9H7)Cl with 1 equiv of Li2C2B10H10 gave, after hydrolysis, the new versatile ligand Me2Si(C9H7)(C2B10H11) (1). 1 can be conveniently converted into the monoanion [Me2Si(C9H6)(C2B10H11)]-(2) and the dianion [Me2Si(C9H6)(C2B10H10)]2-(3) by treatment with 1 equiv or excess amounts of NaH, respectively. Treatment of SmI2 with 2 in THF gave the unexpected redox product [η5:η6-Me2Si(C9H6)(C2B10H11)]Sm(THF)2 (4). Reaction of SmI2 with 1 equiv of 3 in THF, followed by reaction with 2, gave the unexpected C-H bond reduction product [{η5:σ-Me2Si(C9H6)(C2B10H10)}2Sm][Na(THF)6] (5). In contrast, reaction of YbI2 with 1 or 2 equiv of 2 afforded [{η5-Me2Si(C9H6)(C2B10H11)}Yb(σ-I)(THF)2]2 (6) or [η5-Me2Si(C9H6)(C2B10H11)]2Yb(THF)2 (7), respectively. Treatment of YbI2 with 1 equiv of 3 in THF gave [η5:σ-Me2Si(C9H6)(C2B10H10)]Yb(THF)3 (8), which is the first mixed-ligand organolanthanide(II) complex containing both Ln-C ð and ó bonds to be reported. 8 can also be prepared from the reaction of 6 with excess NaH in THF. Reaction of 8 with 1 equiv of 2 in THF yielded [η5-Me2Si(C9H6)(C2B10H11)]Yb(THF)[(μ-η5):σ-Me2Si(C9H6)(C2B10H10)]Na-(THF)3 (9), which can also be prepared by reaction of 7 with 1 equiv of NaH in THF. These new complexes have been fully characterized by 1H, 13C, and 11B NMR, IR spectroscopy, and elemental analyses. The molecular structures of 4, 5, 8, and 9 have been further confirmed by single-crystal X-ray analyses.
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王绍武, Zuowei Xie, *, Shaowu Wang, Zhong-Yuan Zhou, and Thomas C. W. Mak
Organometallics 1999, 18, 1641-1652,-0001,():
-1年11月30日
Reaction of Me2Si(C5H5)Cl with 1 equiv of Li2C2B10H10 in toluene/ether at 0℃, after hydrolysis, gave Me2Si(C5H5)(C2B10H11) (1) in 79% isolated yield. 1 can be conveniently converted into the monoanion [Me2Si(C5H4)(C2B10H11)]Na (2), the dianion [Me2Si(C5H4)-(C2B10H10)]Li2 (3), and the trianion [Me2Si(C5H4)(C2B10H11)]K3 (4) by treatment with NaH, MeLi, and K metal in THF at room temperature, respectively. 2 reacted with 1 equiv of LnCl3 in THF to give [η5-Me2Si(C5H4)(C2B10H11)]LnCl2(THF)3 (Ln) Nd (5), Sm (6), Er (7), Yb (8)) in good yield. Treatment of LnCl3 with 2 equiv of 2 or reaction of [è5-Me2Si(C5H4)-(C2B10H11)]LnCl2(THF)3 with an equimolar amount of 2 in THF resulted in the isolation of [η5-Me2Si(C5H4)(C2B10H11)]2LnCl(THF)2 (Ln) Nd (9), Sm (10), Y (11), Gd (12), Yb (13)) in good yield. Interaction of 3 with LnCl3 in THF in a molar ratio of 1∶1 or 2∶1 or reaction of [η5-Me2Si(C5H4)(C2B10H11)]2LnCl(THF)2 with 2 equiv of MeLi in THF gave the same compounds [{η5:σ-Me2Si(C5H4)(C2B10H10)}2Ln][Li(THF)4] (Ln) Nd (14), Y (15), Er (16), Yb (17)). Treatment of NdCl3 with an equimolar amount of 4 in THF or reaction of [η5-Me2Si-(C5H4)(C2B10H11)]NdCl2(THF)3 with excess K metal in THF produced [η5:η6-Me2Si(C5H4)-(C2B10H11)]Nd(THF)2 (18). Under similar reaction conditions, however, interaction of LnCl3 (Ln) Sm, Yb) with 4 in THF afforded the organolanthanide(Ⅱ) compounds {[η5:η6-Me2Si-(C5H4)(C2B10H11)]LnII(THF)2}{K(THF)2} (Ln) Sm (20), Yb (21)). The Sm analogue of 18, [η5:η6-Me2Si(C5H4)(C2B10H11)]Sm(THF)2 (19), was prepared from an unprecedented redox reaction of SmI2 with 2 equiv of 2 in THF. Reaction of 19 with excess K metal in THF gave 20. Unlike the SmI2 case, interaction of YbI2 with 2 equiv of 2 in THF gave [η5-Me2Si(C5H4)-(C2B10H11)]2YbII(THF)2 (22). All of these compounds were characterized by various spectroscopic and elemental analyses. The solid-state structures of compounds 5, 8, 9, 10, 14, 15, 16, 17, 19, and 22 were confirmed by single-crystal X-ray analyses. The reaction mechanism of the formation of 19 is also proposed.
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王绍武, Zuowei Xie, *, Shaowu Wang, Qingchuan Yang, and Thomas C. W. Mak
Organometallics 1999, 18, 1578-1579,-0001,():
-1年11月30日
Summary: Reaction of Me2Si(C9H7)(C2B10H11) with 4 equiv of NaNH2 in dry THF, followed by treatment with 1 equiv of LnCl3, gave unprecedented tetranuclear clusters of the general formula [{(η5-μ2-C9H6SiMe2NH)-Ln}2(μ3-Cl)(THF)]2(í4-NH)âTHF (Ln) Gd (1), Er (2)) in moderate yield. Their molecular structures have been confirmed by single-crystal X-ray analyses, which represent the first organometallic clusters containing a central μ4-imido group.
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【期刊论文】A New Versatile Ligand: Its Synthesis and Applications in Organolanthanide Chemistry
王绍武, Zuowei Xie, *, Shaowu Wang, Zhong-Yuan Zhou, Feng Xue, and Thomas C. W. Mak
Volume 17, Number 4, February 16, 1998,-0001,():
-1年11月30日
Summary: Treatment of Me2Si(C5H5)Cl with Li2C2B10H10 followed by hydrolysis gave the new versatile ligand Me2-Si(C5H5)(C2B10H11) in 79% isolated yield, which can be converted into the monoanion, dianion, and trianion, respectively. It makes possible the synthesis of a wide range of organometallic complexes.
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王绍武, Shaowu Wang, †, ‡, Hung-Wing Li, and Zuowei Xie*
Organometallics 2004, 23, 3780-3787,-0001,():
-1年11月30日
A new amine-functionalized carboranyl-indenyl hybrid ligand shows unique properties in stabilizing various kinds of lanthanocene chloride complexes via increasing steric effects imposed by the coordination of NMe2 to the central metal ion, leading to the isolation of kinetic products and monomeric neutral species. Treatment of Me2SiCl(C9H6CH2CH2NMe2) with 1 equiv of Li2C2B10H10 afforded the monolithium salt [Me2Si(C9H5CH2CH2NMe2)-(C2B10H11)]Li(OEt2) (2). Interaction of 2 with 1 equiv of n-BuLi produced the dilithium salt [Me2Si(C9H5CH2CH2NMe2)(C2B10H10)]Li2(OEt2)2 (3). Treatment of 3 with 1 equiv of YbCl3 gave [{η5:η1:σ-Me2Si(C9H5CH2CH2NMe2)(C2B10H10)}YbCl2][Li(THF)4] (4). Upon heating, 4 was converted to [{η5:η1:σ-Me2Si(C9H5CH2CH2NMe2)(C2B10H10)}Yb(μ-Cl)1.5]2[Li(THF)4] (6) and finally to [{η5:η1:σ-Me2Si(C9H5CH2CH2NMe2)(C2B10H10)}Yb(í-Cl)]2 (7) via the elimination of LiCl. Treatment of 6 or its Sm analogue 5 with 2 equiv of sodium amide gave [η5:η1:ó-Me2-Si(C9H5CH2CH2NMe2)(C2B10H10)]Yb(NHC6H3-2,6-Pri 2) (9) or [η5:η1:σ-Me2Si(C9H5CH2CH2-NMe2)(C2B10H10)]Sm(μ-NHC6H3-2,6-Pri 2)(μ-Cl)Li(THF) (8). An equimolar reaction of SmI2 with 3 generated, after addition of LiCl, [{η5:η1:η6-Me2Si(C9H5CH2CH2NMe2)(C2B10H10)Sm}2-(μ-Cl)][Li(THF)4] (10). In sharp contrast, a less reactive YbI2 reacted with 3 in THF, producing only the salt metathesis product [η5:η1:σ-Me2Si(C9H5CH2CH2NMe2)(C2B10H10)]Yb(DME) (11). 11 reacted with 1 equiv of 3 to give the ionic complex {[(μ-η5:η2):η1:σ-Me2Si(C9H5CH2CH2-NMe2)(C2B10H10)]2Yb}{Li(THF)2}2 (12). All complexes were characterized by spectroscopic techniques and elemental analyses. Their structures were all further confirmed by singlecrystal X-ray analyses.
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王绍武, Shaowu Wang, †, ‡, Hung-Wing Li, and Zuowei Xie*
Organometallics 2004, 23, 2469-2478,-0001,():
-1年11月30日
New ether-functionalized carboranyl-indenyl hybrid ligands were prepared. They can prevent lanthanocene chlorides from ligand redistribution reactions and offer samarium(Ⅱ) complexes unusual reactivities. Treatment of Me2SiCl(C9H6CH2CH2OMe) with 1 equiv of Li2C2B10H10 in toluene/Et2O afforded the monolithium salt [Me2Si(C9H5CH2CH2OMe)-(C2B10H11)]Li(OEt2) (2). Interaction of 2 with 1 equiv of n-BuLi in Et2O produced the dilithium salt [Me2Si(C9H5CH2CH2OMe)(C2B10H10)]Li2(OEt2)2 (3). Reaction of 3 with 1 equiv of LnCl3 at room temperature gave the complex salts of general formula [{[è5:ó-Me2Si(C9H5CH2CH2-OMe)(C2B10H10)]Ln(THF)(μ-Cl)3Ln[η5:η1:η-e2Si(C9H5CH2CH2OMe)(C2B10H10)]}2{Li(THF)}]-[Li(THF)4] (Ln) Y (4), Yb (5)). Upon heating, 5 was converted into [η5:η1:η-Me2Si(C9H5-CH2CH2OMe)(C2B10H10)]Yb(THF)(μ-Cl)2Yb[η5:η1:η-Me2Si(C9H5CH2CH2OMe)(C2B10H10)] (6) by eliminating LiCl. Treatment of 4 or 5 with 2 equiv of group 1 metal amides gave organorare-earth amide complexes [è5:è1:ó-Me2Si(C9H5CH2CH2OMe)(C2B10H10)]Y(NHC6H3-2,5-tBu2)-(μ-Cl)Li(THF)3 (8) or [η5:η1:η-Me2Si(C9H5CH2CH2OMe)(C2B10H10)]Yb(NHC6H3-2,6-iPr2)(í-Cl)Li(THF)3 (9). An equimolar reaction of SmI2 with 3 in THF generated, after addition of LiCl, [{[è5:η-Me2Si(C9H5CH2CH2OMe)(C2B10H10)]2Sm}{Li(THF)}]n (10) and [{η5:η1:η6-Me2-Si(C9H5CH2CH2OMe)(C2B10H10)Sm}2(í-Cl)][Li(THF)4] (11). In sharp contrast, a less reactive YbI2 reacted with 3 in THF, producing only salt metathesis product [η5:η1:η-Me2Si(C9H5-CH2CH2OMe)(C2B10H10)]Yb(DME)(THF) (12). 12 reacted with 1 equiv of 3 to give the ionic complex {[(μ-η5:η2):η1:η-Me2Si(C9H5CH2CH2OMe)(C2B10H10)]2Yb}{Li(THF)2}2 (13). All complexes were characterized by various spectroscopic techniques and elemental analyses. The structures of 5, 6, and 8-13 were further confirmed by single-crystal X-ray analyses.
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