李晓燕 - 山东大学 - 化学与化工学院

研究领域

金属有机化学，催化化学，有机合成 1、C-H键的活化，M-H键的形成及其反应特性 C-H键的活化是金属有机化学中的“传统”而又充满活力的分支，它是许多有机合成反应和分子转化过程中的关键步骤。过渡金属配合物催化的C-H键的活化由于反应条件温和，选择性高，易于控制和实现，一直是金属有机化学家致力于探索的反应。由于在很多重要的化学过程，如氢甲酰化中的核心作用，使得[Co-H]结构单元的反应特性为化学家格外关注。三甲基膦作为高对称性，具有优良的光谱特征的分子，是十分适宜的辅助配体。利用强Lewis碱三甲基膦支持的Fe、Co和Ni化合物为原料，可实现一系列的C-H键的活化反应。我们研究小组目前主要致力于研究三甲基膦支持的金属有机氢化物的合成，表征及作为模型化合物在碳-碳偶联反应中的作用。 2、铁、钴和镍金属有机氢化物对不饱和键的催化还原作用近年来随着实验技术的进步和人们对绿色化学的期待，过渡金属氢配合物的性质及其在催化反应中的应用越来越受到人们的广泛关注。在已知的过渡金属氢配合物催化体系中多以贵金属，如Rh、Ru、Pt和Pd等等，为中心原子。这些配合物不仅价格高，且多具有一定的毒性，使其工业化应用受到一定的限制。以Fe、Co和Ni为金属中心原子的氢配合物及催化应用的研究报道相对较少。我们研究小组目前主要致力于以Fe、Co和Ni的金属有机氢配合物的设计、合成及其对不饱和键的催化还原作用为研究内容，建立新的以Fe、Co和Ni为中心金属原子的催化体系。选择廉价铁、钴和镍氢化物作为催化剂进行催化研究，不仅对合成化学有重要意义，而且对绿色化学和可持续性发展有很好的推动作用。 3、C-F键的活化及其应用研究 C-F键的活化成为金属有机化学中的研究热点之一，且由于C-F键的高键能，使其成为一个艰难的挑战。开展C-F键活化研究不仅益于寻找新的氟化，脱氟及C-F键功能化途径；同时也对于催化氟降解有很重要的指导意义，在环境保护和绿色化学方面有很好的应用前景。最近，我们利用三甲基膦支持的低价钴的配合物，通过环金属化反应，成功地实现了C-F键的活化，得到了第一个三价钴的金属有机氟化物。开拓了在该领域一个新的研究方向。我们将深入在该领域的研究工作，实现C-F键活化的同时，研究探索合成有机氟化合物的新方法。

近期论文

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Zhao,Hua, Sun, Hongjian and Li, Xiaoyan*, Synthesisand Catalytic Property of IronPincer Complexes Generated by Csp3-H Activation, Organometallics 33,3535-3539,2014. Zuo, Zhenyu, Sun,Hongjian, Wang, Lin and Li,Xiaoyan*,Hydrosilylation of Aldehydes and Ketones Catalyzed by HydridoIronComplexes Bearing Imine Ligands,DaltonTrans., 43,11716-11722,2014. Sun,Yunqiang， Li，Xiaoyan and Sun, Hongjian*,[CNN]-pincer nickel(II)complexes of N-heterocyclic carbene(NHC): synthesis andcatalysis of the Kumada reaction of unactivated C–Clbonds, DaltonTrans., 43, 9410. Zhu,Gengyu, Li, Xiaoyan, Xu,Guoqiang, Wang, Linand Sun, Hongjian * A new PC(sp3)Pligand and its coordination chemistry withlow-valent iron, cobalt and nickel complexes, Dalton Trans.,,43,8595-8598, 2014. Lu, Faguan ; Sun,Hongjian ; Du,Aiqin ; Feng, Lei and Li ,Xiaoyan*, Selective Alkylation andArylation of C−FBond with Grignard Reagents,Org. Lett. 16,772−775, 2014. Sun, Yunqiang ; Sun,Hongjian ;Jia, Jiong ; Du, Aiqin and Li,Xiaoyan*,Transition-Metal-Free Synthesisof Fluorinated Arenes fromPerfluorinated ArenesCoupled with GrignardReagents, Organometallics,33,1079−1081,2014. Niu, Qingfen ; Sun,Hongjian ;Wang, Lin; Hu,Qingping*and Li, Xiaoyan*,Reactivity of mer-hydrido(2-mercaptobenzoyl)tris(trimethylphosphine)cobalt(III)complex, DaltonTrans.,43, 4059–4066, 2014. Li,Junye, Li, Xiaoyan, Wang,Lin,Hu,Qingping*aand Sun, Hongjian *, C–Cl bond activation andcatalytichydrodechlorination of hexachlorobenzene by cobaltand nickel complexeswith sodium formate as a reducing agent,Dalton Trans.,43, 6660-6666, 2014. Li, Jingjing ; Zhang,Dongju* ;Sun, Hongjian and Li, Xiaoyan*,Computational rationalization ofthe selectiveC–H and C–F activations offluoroaromatic imines and ketones bycobaltcomplexes, Org. Biomol. Chem.,12,1897–1907, 2014. Wu, Siquan; Li, Xiaoyan; Xiong, Zichang;Xu, Wengang; Lu, Yunqiang; and Sun Hongjian*, Synthesis and Reactivity of SilylIron, Cobalt, and Nickel Complexes Bearing a [PSiP]-Pincer Ligand via Si−H BondActivation， Organometallics， 32, 3227-3237, 2013. Xu, Wengwng; Sun, Hongjian; Xiong, Zichang; LiXiaoyan*,Acid-Promoted SelectiveCarbon−Fluorine Bond Activation and Functionalization ofHexafluoropropene byNickel Complexes Supported with Phosphine Ligands,Organometallics,32, 7122-7132, 2013. Li, Junye ; Zheng,Tingting ; Sun,Hongjian ; Xu, Wengang and Li,Xiaoyan*, SelectiveC–F/C–H bond activationof fluoroarenes by cobalt complexsupported withphosphine ligands, DaltonTrans., 42,5740–5748, 2013. Li, Junye ; Zheng,Tingting ; Sun,Hongjian and Li, Xiaoyan*,Selectively catalytichydrodefluorination ofperfluoroarenes by Co(PMe3)4withsodium formate asreducing agent and mechanism study, Dalton Trans.,42,13048–13053, 2013. Niu, Qingfen ; Sun,Hongjian ; Li , Xiaoyan* ; Klein, H.-F. ; Floerke,Ulrich,Synthesis and Catalytic Application inHydrosilylation oftheComplexmer-Hydrido(2-mercaptobenzoyl)tris(trimethylphosphine)cobalt(III), Organometallics,32,5235−5238,2013. Xu, Xiaofeng; Jia, Jiong;Sun, Hongjian; Liu,Yuxia; Xu,Wengang; Shi, Yujie;Zhang, Dongju*; Li Xiaoyan*,SelectiveActivation of C-F and C-H Bonds with IronComplexes, the RelevantMechanismStudy by DFT Calculations and Study on theChemical Properties ofHydrido IronComplex, Dalton Trans., 42, 3417-3428, 2013. Liu, Nazhen; Zhu, Gengyu;Sun, Hongjian; Li, Xiaoyan*,Simple synthesis andstructure characterization of aphosphoniomethylidynetantalum(V) complex, Inorg.Chem. Commun., 27,36-39, 2013. Zhang, Zehua; Sun, Hongjian;Xu, Wengang; Li,Xiaoyan*, N-H bond activation of2-aminobenzophenone bytrimethylphosphinecomplexes of nickel and cobalt, Polyhedron, 50,571-575. 2013. Niu, Qingfen;Lu,Yunqiang; Sun, Hongjian; Li, Xiaoyan1*; Tao, Xutang2*,Novelphenyl-oligothiophenederivatives containing acetylenic spacers for thinfilmmaterials: synthesis,photophysical and morphology properties,Dyesand pigment, 97，184-197, 2013. Yang, Xiuxiu; Sun,Hongjian;Zhang, Shumiao; Li, Xiaoyan*, Nickel-catalyzed C-Fbond activationand alkylationof polyfluoroaryl imines, J.Organomet.Chem.,, 723, 36-42, 2013. Zheng, Tingting; Sun,Hongjian; Lu,Faguan; Harms, Klaus; Li, Xiaoyan*, Cobaltinduced C-H BondActivation andC8-Arylation of Caffeine with Aryl Bromides, Inorg.Chem.Commun.,30, 139-142, 2013. Niu, Qingfen;Lu,Yunqiang; Sun, Hongjian; Li, Xiaoyan1*; Tao, Xutang2*,Novelplanar and star-shaped molecules:synthesis, electrochemical andphotophysicalproperties, Spectrochimica ActaPart A: Molecular andBiomolecularSpectroscopy, 377-385, 2013. Niu, Qingfen; Xu,Xiaofeng; Sun, Hongjian; Li,Xiaoyan*, Synthesis of2-Mercaptobenzaldehyde, 2-Mercaptocyclohex-1-enecarboxaldehydesand3-Mercaptoacrylaldehydes,Chin. J. Chem., 30, 2495-2500,2012. Xu, Xiaofeng; Sun,Hongjian; Shi, Yujie; Jia,Jiong*, Li,Xiaoyan*,Imine-assisted C-F bondactivation by electron-rich iron complexessupported bytrimethylphosphine,DaltonTrans., 40,7866-7872,2011. Wang, Chenggen; Sun,Hongjian; Hu, Qingping;Li, Xiaoyan*,CarbonylativeFormationofN-Acetyl-2,6-difluorobenzamide through N-H BondActivationof2,6-Difluorobenzamide with Ni(II) Complex Supported with PhosphineLigands, J.Organomet.Chem., 696, 2815-2819, 2011. Liu, Nazhen; Li,Xiaoyan; Sun, Hongjian*, Synthesis and propertiesof novelortho-metallatedcobalt(I) and iron(II) complexes through Csp2-H bondactivationofdibenzylphenylphosphine, J.Organomet. Chem.,696,2537-2542, 2011. Lian, Zhe; Xu,Xiaofeng; Sun, Hongjian; Chen,Yue; Zheng, Tingting; Li, Xiaoyan*，Imine-assisted C-F bond activation usinglow-valentcobaltcompounds supported by trimethylphosphineligands and formationof novelorganicfluorides，Dalton Trans., 39,9523-9529,2010. Zheng, Tingting; Sun,Hongjian; Ding, Jun;Zhang, Yanfeng; Li, Xiaoyan*, Effectof anchoring group andvalent of cobaltcenter on the competitive cleavage ofC-F bond activation, J.Organomet. Chem.,695, 1873-1877, 2010. Zheng,Tingting; Li, Min;Sun,Hongjian; Harms, Klaus; Li, Xiaoyan*, Synthesisof newthiophenolato hydridoiron(II) complexes and their substitutionreactions withalkynes. Polyhedron,28(17), 3823-3827, 2009. Xu, Guoqiang;Sun, Hongjian;Li,Xiaoyan*, Activation of sp3Carbon-Hydrogen Bonds by Cobalt andIronComplexes and Subsequent C-C BondFormation. Organometallics,28(20),6090-6095, 2009. Zheng,Tingting; Sun,Hongjian;Chen, Yue; Li, Xiaoyan*; Durr, Simon; Radius, Udo;Harms, Klaus,Synergistic Effect of a Low-Valent CobaltComplex and aTrimethylphosphineLigand on Selective C-F Bond Activation ofPerfluorinatedToluene. Organometallics,28(19), 5771-5776, 2009."