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Recent developments in homobimetallic reagents and catalysts for organic synthesis

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Chinese Science Bulletin 2011年第17期56卷 1753-1769页

作者： WU Wei GU DeLiang WANG ShiMeng ning yingnan MAO GuoLiang Provincial Key Laboratory of Oil and Gas Chemical Technology College of Chemistry and Chemical Engineering Northeast Petroleum University Daqing 163318 China

Organometallics are a family of useful organic chemicals because they play important roles in organic synthesis as reagents and as *** can be classified according to the number of metals they *** compounds are important organometallics and they are either homobimetallic or heterobimetallic depending on whether the two metals are the same or *** this paper,we focus on homobimetallic *** compounds are generally used as dianions to react with electrophiles in organic ***,homobimetallics have also been used as catalysts in organic reactions such as in asymmetric reactions.

关键词：有机合成试剂催化剂有机金属化合物有机化工原料双金属化合物有机反应不对称反应数量分类

Recent progresses of late-transition metal complexes with nonsymmetric diimine ligands in ethylene polymerization and oligomerization

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Chinese Science Bulletin 2014年第21期59卷 2505-2512页

作者： Guoliang Mao Yue Jiang ning Li Qin Wang Dejin Zheng Meijiao Li yingnan ning Provincial Key Laboratory of Oil & Gas Chemical Technology College of Chemistry and Chemical EngineeringNortheast Petroleum University

Researches of late-transition metal complexes for ethylene polymerization and oligomerization have attracted a lot of attention in the last two decades.A large number of late-transition metal complexes with symmetric diimine ligands have been extensively *** the research of unsymmetric diimine late-transition metal complexes was still in the initial stage,some superior performances were observed in olefin *** developments in the research of ethylene polymerization and oligomerization catalyzed by late-transition metal complexes with unsymmetric diimine ligands were summarized in this review,with the influence of complex structure on the catalytic performance of the catalyst analyzed.

关键词：过渡金属配合物乙烯聚合二亚胺非对称后期齐聚配体聚合反应速率

Boron- and silicon-bridged bis(diphenylphosphino)-type ligands for chromium-catalyzed ethylene oligomerization

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Chinese Science Bulletin 2014年第21期59卷 2613-2617页

作者： Yueming Sun Yanhui Chen Guoliang Mao yingnan ning Tao Jiang College of Material Science and Chemical Engineering Tianjin University of Science & Technology College of Chemistry and Chemical Engineering Northeast Petroleum University

PNP-type ligands showed very good property in the catalytic systems of PNP/Cr(Ⅲ)/methylaluminoxane(MAO)for ethylene selective tetramerization *** this research,two PNP analogues bis(diphenylphosphino)phenylborane and bis(diphenylphosphino)dimethylsilane have been synthesized and *** combination with CrCl3(THF)3as active center and MAO as cocatalyst,these ligands produced a new catalytic systems for ethylene oligomerization to linear α-olefins with catalytic activities of up to 3.07 9 106g mol-1(cat)***,we report the effects of the reaction temperature,ethylene pressure,and the molar ratio of Al/Cr on the catalyst activities and product selectivities.

关键词：二苯基膦催化体系乙烯低聚配体硅桥连 PNP型铬

Effect of Alkylaluminum Activators on Ethylene Trimerization Based on 2,5-DMP/Cr（III）/TCE Catalyst System

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Chinese Journal of Chemistry 2011年第6期29卷 1149-1153页

作者： Jiang, Tao Ji, Rongxin Chen, Hongxia Cao, Chengang Mao, Guoliang ning, yingnan College of Material Science and Chemical Engineering Tianjin University of Science & Technology Tianjin 300457 China Department of Chemistry and Chemical Engineering Northeast Petroleum University Daqing HeUongjiang 163318 China

Ethylene trimerization toward 1-hexene catalytic system with 2,5-dimethylpyrrole （2,5-DMP）/Cr（III）/alkylaluminum/tetrachloroethane （TCE） was investigated. The effects of various cocatalysts on catalytic activity and product selectivity were discussed. The results showed that triethylaluminum （TEA）, trimethylaluminum （TMA）, tri-n-hexylaluminum （TNHA） and tri-isobutylaluminum （TIBA） were all effective cocatalysts for ethylene trimerization toward 1-hexene. 2,5-DMP/Cr（III）/TEA/TCE catalytic system afforded the best results for ethylene trimerization, while reducing the level of by-product formation. Some specific interaction modes of alkylaluminum with active Cr species in the catalytic cycle were proposed to explain the effect of cocatalyst on catalytic activity and 1-hexene selectivity.

关键词： ethylene oligomerization cocatalyst coordination modes

Ethylene polymerization by novel highly active iron/acetyl(imino)pyridyl complex

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Chinese Science Bulletin 2006年第18期51卷 2197-2200页

作者： JIANG Tao ning yingnan HU Wenbo WANG Libo HUANG Zhijun LIU Xiaoyu School of Chemistry and Chemical Engineering Daqing Petroleum Institute Daqing 163318 China

Novel iron-based complex and ace- tyl(imino)pyridine iron(II) chloride (1 and 2) have been successfully synthesized and characterized. The behavior of the complex/methylaluminoxane (MAO) for ethylene polymerization was investigated and compared with 2,6-Bis(imino)pyridyl iron(II) chloride (3 and 4)/MAO. The results show that the new ace- tyl(imino)pyridine iron(II) chloride/MAO catalytic sys- tems were highly active for ethylene polymerization. Polyethylene from those polymerization systems has a bimodal molecular weight distribution (MWD).

关键词：后转变金属铁复合物催化剂乙烯聚合

A series of novel bisphosphinoamine ligands:Synthesis,characterization and application in ethylene tetramerization

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Chinese Science Bulletin 2010年第33期55卷 3750-3754页

作者： JIANG Tao CHEN HongXia CAO ChenGang MAO GuoLiang ning yingnan College of Material Science and Chemical Engineering Tianjin University of Science & Technology Tianjin 300457 China Department of Chemistry and Chemical Engineering Daqing Petroleum Institute Daqing 163318 China

A series of novel N-halogen-substituted-aryl bisphosphinoamine ligands were synthesized and characterized by elemental analysis,1H NMR and mass *** combination of these ligands with Cr(Ⅲ) and activation by methylaluminoxane leads to highly active catalytic systems for the tetramerization of ethylene to form *** catalytic activities and product selectivi-ties depend on the aryl ring substituents and the reaction *** found that the location and size of the substituents are important in determining the catalytic activity and selectivity toward *** trend is similar to that observed for their alkyl-substituted analogues.

关键词：催化体系配体合成乙烯表征甲基铝氧烷元素分析核磁共振

Recent progress in immobilization of late-transition-metal complexes with diimine ligands for olefin polymerization

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Chinese Science Bulletin 2013年第15期58卷 1741-1750页

作者： WU Wei JIANG Yan WU Hao LV ChunSheng LUO MingJian ning yingnan MAO GuoLiang Provincial Key Laboratory of Oil and Gas Chemical Technology College of Chemistry and Chemical EngineeringNortheast Petroleum University

Late-transition-metal(LTM) catalysts are a family of very flexible ethylene polymerization catalysts because their catalytic performance can be easily adjusted by modifying the ligand *** less oxyphilicity character,which may promote the production of copolymers from ethylene and polar comonomers,is another aspect that attracts much attention in both academic and industrial *** immobilization of LTM catalysts on spherical supports is a crucial step prior to their use in the industrial processes of gas-phase or slurry *** paper reviews recent developments in supported LTM catalysts for olefin polymerization,and summarizes loading methods and mechanisms of the immobilization of LTM catalysts on inorganic,organic,and inorganic-organic materials,and the effects of immobilization on catalytic activity,polymerization mechanism,and polymer morphology.

关键词：后过渡金属配合物烯烃聚合配体亚胺催化剂聚合反应催化性能共聚单体

Ethylene tetramerization with a highly active and long-lifetime trinuclear diphenylphosphinoamine/Cr(III)/MAO catalyst

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Chinese Science Bulletin 2012年第13期57卷 1510-1515页

作者： JIANG Tao TAO YiQing GAO XiangLu MAO GuoLiang CHEN HongXia CAO ChenGang ning yingnan College of Material Science and Chemical Engineering Tianjin University of Science&TechnologyTianjin 300457China Department of Chemistry and Chemical Engineering Northeast Petroleum UniversityDaqing 163318China

The synthesis and characterization of a novel trinuclear diphosphinoamine ligand 2 are reported. The ligand combined with Cr(III), activated with methylaluminoxane, lead to highly active and long-lifetime catalytic systems for the tetramerization of ethylene to form 1-octene. The effects of reaction temperature, reaction pressure, molar ratio of Al/Cr and bis(diphenylphosphino)amine/Cr on the catalytic activity and product selectivity were studied. Compared with its mononuclear analogue 1, ligand 2 showed a higher catalytic activity and longer lifetime for ethylene tetramerization in the presence of methylaluminoxane as cocatalyst. High molecular weight polyethylene was generated as a by-product with extremely broad molecular weight distributions.

关键词：乙烯产生铬(Ⅲ) 助催化剂长寿命高活性三核甲基铝氧烷双膦配体

Synthesis of a novel triple-site diphosphinoamine (PNP) ligand and its applications in ethylene tetramerization

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Chinese Science Bulletin 2008年第22期53卷 3511-3515页

作者： MAO GuoLiang ning yingnan HU WenBo LI ShanMing SONG XianFeng NIU Bo JIANG Tao Department of Chemistry and Chemical Engineering Daqing Petroleum Institute Daqing 163318 China

A novel triple-site diphosphinoamine (PNP) ligand was synthesized and characterized. In combination with Cr(III) and methylaluminoxane (MAO), it generated active catalytic systems for ethylene tetramerization toward 1-octene with high catalytic activity and long lifetime. The effects of reaction temperature, molar ratio of Al/Cr and molar ratio of ligand/Cr on catalytic activity and selectivity to 1-octene were studied with reaction kinetics of the catalytic system for ethylene tetramerization described. At the Al/Cr molar ratio of 100, the catalytic activity is up to 2.29×106 g·mol-1 (Cr)·h-1 and the selectivity to 1-octene is 49.65 wt%.

关键词： PNP 乙烯化作用 MAO 化学分析