含氮（氧）有机配体及其金属化合物的合成与结构
摘要
金属有机化学是融合有机化学与无机化学的一门交叉学科,发展最为活跃、迅速、富有生命力,是当代化学的前沿领域之一。伴随绿色化学的兴起,合成一类无毒、无污染的多功能配合物成为当今金属有机化学的一个研究热点。
正是基于以上研究背景,本论文设计并合成了一系列新型的金属有机化合物,以期用于丙交酯的开环聚合得到良好的催化效果。主要内容分为以下三章:
第一章为导论,介绍了本论文工作的研究背景,分为三部分:(1)胍基金属有机化合物的研究进展;(2)β-二亚胺金属有机化合物的性质、合成与催化应用;(3)丙交酯开环聚合合成聚乳酸的研究进展,包括对催化剂类型,催化机理,催化效果等方面的分析与探索。
第二章分别以芳香胺(邻苯二胺、间苯二胺、对苯二胺)和脂肪胺(乙二胺)为例,探讨了胍基配体及其金属有机化合物的合成方法,并且对一意外得到的极为对称的脒基锂盐进行了反应机理研究,最后利用NMR、元素分析、X-Ray单晶衍射仪和熔点测定仪等各种技术手段对所得化合物的结构、性质进行分析表征。
第三章简单介绍了β-二亚胺类金属有机化合物的研究进展,并且以文献中报道的最经典的β-二亚胺化合物为原料合成了一系列β-二亚胺配体及其金属有机化合物,最后利用NMR、元素分析、X-Ray单晶衍射仪和熔点测定仪等各种技术手段对所得化合物的结构、性质进行分析表征。
最后对本论文所有工作的得失进行了回顾与总结,同时提出了我们未来工作的具体计划,希望我们在不断的努力中获得更有效的成果。
Organometallic chemistry is a cross-science of organic chemistry and inorganic chemistry and one of the important branches in the modern chemistry, which is developing most actively, promptly and full of vitality. With the rising of green chemistry, synthesis of nontoxic and noncontaminative organometallic compounds as new materials or catalysts has become a hot topic of organometallic chemistry.
Based on the background of the above research, we designed and synthedized a series of new organometallic complexes to seek the excellent catalysts for the ring-opening polymerization (ROP) of lactide. The details are listed as follws:
Chapter 1.The background of the research work was introduced. It was divided into three sections: (1) The progress of guanidinato-metal complexes; (2) The progress ofβ-diimido-metal complexes in organic synthesis, catalysis and properties; (3) Progress of ring-opening polymerization (ROP) of lactide, including synthesis and reaction mechanisms.
Chapter 2. Synthesis of guanidinato ligands and their metallic complexes was discussed and their structural characterizations were studied by NMR, elemental analysis and X-ray diffraction analysis.
Chapter 3. The progress ofβ-diketiminato organometallic compounds were introduced and a series ofβ-diketiminato ligands and their metal complexes were synthedized and characterized.
正是基于以上研究背景,本论文设计并合成了一系列新型的金属有机化合物,以期用于丙交酯的开环聚合得到良好的催化效果。主要内容分为以下三章:
第一章为导论,介绍了本论文工作的研究背景,分为三部分:(1)胍基金属有机化合物的研究进展;(2)β-二亚胺金属有机化合物的性质、合成与催化应用;(3)丙交酯开环聚合合成聚乳酸的研究进展,包括对催化剂类型,催化机理,催化效果等方面的分析与探索。
第二章分别以芳香胺(邻苯二胺、间苯二胺、对苯二胺)和脂肪胺(乙二胺)为例,探讨了胍基配体及其金属有机化合物的合成方法,并且对一意外得到的极为对称的脒基锂盐进行了反应机理研究,最后利用NMR、元素分析、X-Ray单晶衍射仪和熔点测定仪等各种技术手段对所得化合物的结构、性质进行分析表征。
第三章简单介绍了β-二亚胺类金属有机化合物的研究进展,并且以文献中报道的最经典的β-二亚胺化合物为原料合成了一系列β-二亚胺配体及其金属有机化合物,最后利用NMR、元素分析、X-Ray单晶衍射仪和熔点测定仪等各种技术手段对所得化合物的结构、性质进行分析表征。
最后对本论文所有工作的得失进行了回顾与总结,同时提出了我们未来工作的具体计划,希望我们在不断的努力中获得更有效的成果。
Organometallic chemistry is a cross-science of organic chemistry and inorganic chemistry and one of the important branches in the modern chemistry, which is developing most actively, promptly and full of vitality. With the rising of green chemistry, synthesis of nontoxic and noncontaminative organometallic compounds as new materials or catalysts has become a hot topic of organometallic chemistry.
Based on the background of the above research, we designed and synthedized a series of new organometallic complexes to seek the excellent catalysts for the ring-opening polymerization (ROP) of lactide. The details are listed as follws:
Chapter 1.The background of the research work was introduced. It was divided into three sections: (1) The progress of guanidinato-metal complexes; (2) The progress ofβ-diimido-metal complexes in organic synthesis, catalysis and properties; (3) Progress of ring-opening polymerization (ROP) of lactide, including synthesis and reaction mechanisms.
Chapter 2. Synthesis of guanidinato ligands and their metallic complexes was discussed and their structural characterizations were studied by NMR, elemental analysis and X-ray diffraction analysis.
Chapter 3. The progress ofβ-diketiminato organometallic compounds were introduced and a series ofβ-diketiminato ligands and their metal complexes were synthedized and characterized.
引文
[1]覃远根.浅谈金属有机化学的研究方向.科技信息,2007,24,34.
[2]Zeise,W.C.,Ann.Phys.,1827,9,632-635.
[3]张立新.黄祖恩,周锡庚,马怀柱.稀土金属有机化学的发展概况.上海化工.1998,6,37-39.
[4]白峰,李弘.胍在不对称合成中的应用.有机化学,2004,24,1532-1541.
[5]Ohtani,I.;Kusumi,T.;Kajusawa,H.;Kashman,Y.;and Shulamit,H.,Structure and Chemical Properties of Ptilomycalin A,J Am Chem Soc,1992,114,8472-8479.
[6]宋伟,陆晓峰,陆国元.间二苄胍衍生物的合成.高等学校化学学报,2006,27,460-463.
[7]Bailey,P.J.;Pace,S.,The coordination chemistry of guanidines and guanidinates.,Coord Chem Rev,2001,214,91-141.
[8] (1)Gobel, M.; Klapotke, T. M., et al. First structural characterization of guanidine, HN=C(NH_2)(2), Chem Commun., 2007, (30):3180-3182.
[9] Sotome, Y.; Takemura, N., et al. Organocatalytic asymmetric nitroaldol reaction: Cooperative effects of guanidine and thiourea functional groups, Chemistry-An Asian Journal, 2007,2, 1150-1160.
[10] Rodriguez, F.; Rozas, I., et al. Guanidine and 2-aminoimidazoline aromatic derivatives as alpha(2)-Adrenoceptor antagonists, 1:Toward new antidepressants with heteroatomic linkers, J Med Chem, 2007, 50,4516-4527.
[11] Maiti, K. K.; Lee, W. S., et al. Guanidine-containing molecular transporters: Sorbitol-based transporters show high intracellular selectivity toward mitochondria, Angew Chem Int Ed, 2007, 46, 5880-5884.
[12] Gerard, B.; Denis, G; Pierre, S. J., et al. Pentaalkylguanidines as etherification and esterification catalysts, Tetrahedron, 1990, 46, 1839-1848.
[13] Zhang, W. X.; Nishiura, M., et al. Catalytic addition of amine N-H bonds to carbodiimides by half-sandwich rare-earth metal complexes: Efficient synthesis of substituted Guanidines through amine protonolysis of rare-earth metal guanidinates, Chem EurJ, 2007,13, 4037-4051.
[14] Parks, J. E., Holm, R. H., Synthesis, solution stereochemistry, and electron delocalization properties of bis(β-iminoamino)nickel(II) complexes, Inorg. Chem., 1968, 7, 1408-1416.
[15] Hichcock, P. B., Lappert, M. F., Liu, D. S., (a) Transformation of the bis (trime thylsilyl)methyl into a β-diketinimato ligand; the X-ray structure of [Li(L'L')]_2, SnCl(Me)_2(L'L') and SnCl(Me)_2(L'L'), [L'L'=N(R)C(Ph)C(H)C(Ph)- LL=N(H)C(Ph) C(H)C(Ph)NH,R=SiMe_3],J.Chem.Soc.,Chem.Commun.,1994, 1699-1700. (b) Transformation of the bis -(trimethylsilyl)methyl into aza-allyl and β-diketinimato ligands; the X-ray structures of [Li{N(R)C(Bu~t)CH(R)}]_2 and [Zr{N(R)C (Bu~t)CH C(Ph)N(R)}Cl_3] (R=SiMe_3), J. Chem. Soc, Chem. Commun., 1994, 2637- 2638
[16]Ziniuk,Z.,Goldberg I.,Kol M.,Zirconium complexes of chelating dianionic bis -(pentafluorophenylamido) ligands:synthesis,structure and ethylene polymerisation activity,Inorg.Chem.Commun.,1999,2,549-551.
[17]Liang,L.-C.,Schrock,R.R.,Davis,W.M.,McConvelle,D.H.,Synthesis of Group 4Complexes that Contain the Diamidoamine Ligands,[(2,4,6-Me_3C_6H_2NCH_2CH_2)_2NR]_2-([Mes_2N_2NR]~(2-);R=H or CH_3),and Polymerization of 1-Hexene by Activated [Me_2N_2NR]ZrMe_2 Complexes,J.Am.Chem.Soc.,1999,121,5797-5798.
[18]Graf,D.D.,Schrock,R.R.,Daves,W.M.,Stumpf,R.,Synthesis of Zirconium Complexes Containing the Tridentate Diamido Ligands[(t-Bu-d_6-N-o-C_6H_4)_2S]~(2-) and [(i-PrN-o-C_6H_4)_2S]~(2-),Organometallics,1999,18,843-852.
[19]Mack,H.and Eisen,M.S.,Synthesis,characterization and reactivity of amido titanium and zirconium complexes,J.Organomet.Chem.,1996,525,81-87.
[20]Tshuva,E.Y.,Goldberg,I.,Kol,M.,Goldschmidt,Z.,Zirconium Complexes of Amine -Bis(phenolate) Ligands as Catalysts for 1-Hexene Polymerization:Peripheral Structural Parameters Strongly Affect Reactivity,Organometallics,2001,20,3017-3028.
[21]Tshuva,E.Y.,Goldberg,I.and Kol,M.,Isospecific Living Polymerization of 1-Hexene by a Readily Available Nonmetallocene C_2-Symmetrical Zirconium Catalyst,J.Am.Chem.Soc.,2000,122,10706-10707.
[22]Hichcock,P.B.,Lappert,M.F.,Liu,D.S.,(a) Transformation of the bis(trimethylsilyi)methyl into a β-diketinimato ligand;the X-ray structure of [Li(L'L')]_2,SnCl(Me)_2(L'L') and SnCl(Me)_2(L'L'),[L'L'=N(R)C(Ph)C(H)C(Ph)NR,LL=N(H)C(Ph)C(H)C(Ph)NH,R=SiMe_3),J.Chem.Soc.,Chem.Commun.,1994,1699-1700;
(b) Transformation of the bis -(trimethylsilyl)methyl into aza-allyl and β-diketinimato ligands;the X-ray structures of[Li{N(R)C(Bu~t)CH(R)}]_2 and [Zr{N(R)C(Bu~t)CHC(Ph)N(R)}Cl_3](R=SiMe_3),J.Chem.Soe.,Chem.Commun.1994,2637-2638.
[23]Paulmier,C.,Mollier,Y.,Lozac'h,N.,Bull.Soc.Chim.Fr.,1965,2463.
[24]Kulichenlo,A.V.,Kurbatov,V.P.,Kukharicheva,E.S.,Osipov,O.A.,J.Gen.Chem.,USSR,1985,55,612.
[25]Maraval,A.,Arquier,D.,Igau,A.,Coppel,Y.,Donnadieu,B.,Majoral,J.-P.,Malonodinitrile CH_2(CN)_2 as Synthon for the Preparation of Unprecedented N-Metalla- and N-Phosphino-β-diimine Ligands,Organometallics,2001,20,1716-1718.
[26]Fustero,S.,de la Torre,M.G.,Pina,B.,Fuentes,A.S.,New Strategies for the Synthesis of Fluorinated Vinylogous Amidines and β-Enamino Ketones,J.Org.Chem.,1999,64,5551-5556.
[27]Yokota,S.,Tachi,Y.,Nishiwaki,N.,Ariga,M.,Itoh,S.,A New β-Diketiminate Ligand Carrying a Functional Group on the Carbon Framework.Synthesis and Characterization of a Linear Polymeric Copper(Ⅰ) Complex,Inorg.Chem.,2001,40,5316-5317.
[28]Bradley,D.C.,Thomas,I.M.,Proc.Chem.Soc.,1959,225-226.
[29]Feldman,J.,Mclain,S.J.,Parthasarathy,A.,Marshall,W.J.,Calabrese,C.J.,Arthur,S.D.,Electrophilic Metal Precursors and a β-Diimine Ligand for Nickel(Ⅱ)- and Palladium(Ⅱ)- Catalyzed Ethylene Polymerization,Organometallics,1997,16,1514.
[30]Cui,C.,Roesky,H.W.,Schmidt,H.-G.,Moltemeyer,M.,Hao,H.,Cimpoesu,F.,[HC{(CMe)(NAr)}_2]Al[(NSiMe_3)_2N_2](Ar=2,6-iPr_2C_6H_3):The First Five-Membered AlN_4 Ring System,Angew.Chem.,Int.Ed,2000,39,4531-4533.
[31]Hardman,N.J.,Eichler,B.E.,Power,P.P.,Synthesis and characterization of the monomer Ga{(NDippCMe)_2CH}(Dipp=C_6H_3Pr_2~i-2,6):a low valent gallium(ⅰ) carbene analogue,Chem.Commun.,2000,1991-1992.
[32]Stender,M.,Phillips,A.D.,Power,P.P.,Characterization and Bonding of the Cation [Ge{N(C_6H_3-2,6-i-Pr_2)CMe}_2CH]~+:Comparison with the Isoelectronic Ga{N(C_6H_3-2,6-i-Pr_2)-CMe}_2CH,Inorg.Chem.,2001,40,5314-5315.
[33]Fekl,U.,Kaminsky,W.,Goldberg,K.I.,A Stable Five-Coordinate Platinum(Ⅳ) Alkyl Complex,J..Am.Chem.Soc.,2001,123,6423-6424.
[34]Gibson,V.C.,Maddox,P.J.,Newton,C.,Redshaw,C.,Solan,G.,White,A.J.P.,Williams,D.J.,Maddox,P.J.,Chromium(Ⅲ) complexes bearing N,N-chelate ligands as ethene polymerization catalysts,Chem.Commun.,1998,1651-1652.
[35]Holland,P.L.,Tolman,W.B.,A Structural Model of the Type 1 Copper Protein Active Site:N2S(thiolate)S(thioether) Ligation in a Cu(Ⅱ) Complex,J.Am.Chem.2000,122,6331-6332.
[36]Chamberlain,B.M.,Cheng,M.,Moore,D.R.,Ovitt,T.M.,Lobkovsky,E.B.,Coate,G.W.,Polymerization of Lactide with Zinc and Magnesium β-Diiminate Complexes:Stereocontrol and Mechanism,J.Am.Chem.Soc.,2001,123,3229-3238.
[37]Dove,A.P.,Gibson,V.C.,Marshall,E.L.,White,A.J.P.,Williams,D.J.,A well defined tin(ii) initiator for the living polymerization of lactide,Chem.Commun.,2001,283-284.
[38]Cheng,M.,Moore,D.R.,Reczek,J.J.,Chamberlain,B.M.,Lobkovsky,E.B.,Coate,G.W.,Single-Site β-Diiminate Zinc Catalysts for the Alternating Copolymerization of CO2and Epoxides:Catalyst Synthesis and Unprecedented Polymerization Activity,J.Am.Chem.Soc.,2001,123,8738-8749.
[39]张宗勇,闫玉华.聚乳酸在生物医学领域中的应用,精细与专用化学品,2005,13,7-10.
[40]Das,K.G.,Controlled release technology bioengineering aspects.New York:JohnWiley and Sons,1983.
[41]俞耀庭,张兴栋.生物医用材料,天津:天津大学出版社,2000.181.
[42]牛旭锋,王远亮,罗彦凤,石梁平.内消旋丙交酯及其聚合物的研究进展,高分子材料科学与工程.2005,21,4,34-36.
[43]Williams,C.K.;Brooks,N.R.;Tolman,W.B.,Metalloenzyme inspired dizinc catalyst for the polymerization of lactide,Chem.Commun.,2002,2132-2133.
[44]Wu,J.C.;Yu,T.L.,Recent developments in main group metal complexes catalyzed/initiated polymerization of lactides and related cyclic esters.Coordination Chemistry Reviews.2006,250,602-626.
[45]姚英明,沈琪.二(2,6-二叔丁基-4-甲基苯氧基)钐催化丙交酯开环聚合,应用化学,1998,15,62-64.
[46]崔冬梅,程建华,朱宁,唐涛,陈文启,黄葆同.二价茂稀土配合物催化左旋丙交酯的开环聚合,科学通报,2002,47,418-420.
[47]刘小兰,赵茹,刘晓红,岳俊杰,陈克,缪方明.新型桥连双锌配合物的合成和结构,化学学报,2003,61,578-583.
[48]沈之荃,孙俊全,吴良江,吴兰亭.稀土配位催化合成聚乳酸,化学学报,1990,48:686-689.
[49]袁福根.桥联双金属稀土配合物对丙交酯的催化聚合研究,铁道师范学报,1999,16,4,38-41.
[50]Ford,T.M.;Drysdale N.E.,ACS Polymer Prep,1992,33,463-475.
[51]王小莺,廖凯荣,全大萍,伍青.醇铁化合物引发丙交酯开环聚合机理的研究,中山大学学报(自然科学版),2005,44,42-45.
[52]张杰,胡平,周新林,甘志华.丙交酯的制备及其开环聚合,吉林工业大学学报.1998,28,266-270.
[1]白峰,李弘.胍在不对称合成中的应用.有机化学,2004,24:1532-1541.
[2]宋伟,陆晓峰,陆国元.间二苄胍衍生物的合成.高等学校化学报,2006,27,460-463.
[3]Ohtani,I.;Kusumi,T.;Kajusawa,H.;Kashman,Y.;and Shulamit,H.,Structure and Chemical Properties of Ptilomycalin A,J Am Chem Soc,1992,114,8472-8479.
[4]Gobel,M.;Klapotke,T.M.,et al.First structural characterization of guanidine,HN=C(NH_2)(2),Chem Commun.,2007,(30):3180-3182.
[5]Sotome,Y.;Takemura,N.,et al.Organocatalytic asymmetric nitroaldol reaction:Cooperative effects of guanidine and thiourea functional groups,Chemistry-An Asian Journal,2007,2,1150-1160.
[6]Paul A.Boguszewski,Shahzard S.Rahaman,A Ganesan.Modular three-component solid-phase synthesis of unsymmtrical guanidines via resin capture of carbodiimides.J.Comb.Chem,2004,6(1),32-34.
[7]Christoph W.Zapf,Murray Goodman.Synthesis of 2-amino-4-pyrimidinones from resin-bound guanidines prepared using bis(allyloxycarbonyl)-protected triflylguanidine.J.Org.Chem.,2003,68(26),10092-10097.
[8]Masahiro Terada,Takashi lkehara,Hitoshi Ube.Enantioselective 1,4-addition reactions of diphenyl phosphite to nitroalkenes catalyzed by axially chiral guanidine,J.Am.Chem.Soc,2007,129(46)
[9]Craig A.Miller,Robert A.Batey.Hetero Diels-AIder reactions of nitrosoamidines:an efficient method for the synthesis of functionalized guanidines.Org.Lett.2004,6(5),699-702.
[10]Hao Shen,Zuowei Xie.Titanacarborane amide catalyzed transamination of guanidines.Organometallics 2008,27,2685-2687.
[11]Jing Li,Wan-Yi Jiang,Ke-Li Han.Density functional study on the mechanism of bicyclic guanidine-catalyzed Strecker reaction.J.Org.Chem.2003,68,8786-8789.
[1](a) Edelmann,F.T.,Angew.Chem.Int.Ed,1995,34,2466;
(b) Edelmann,F.T.,Freckmann,D.M.,Schumann,M.H.,Synthesis and Structural Chemistry of Non-Cyclopentadienyl Organolanthanide Complexes,Chem.Rev.,2002,102,1851-1896;
(c) Piers,W.E.,Emslie,D.J.H.,Non-cyclopentadienyl ancillaries in organogroup 3 metal chemistry:a fine balance in ligand design,Coord.Chem.Rev.,2002,233-234,131-155.
[2]Feldman,J.,McLain,S.J.,Parthasarathy,A.,Marshall,W.J.,Calabrese,C.J.,Arthur,S.D.,Electrophilic Metal Precursors and a β-Diimine Ligand for Nickel(Ⅱ)-and Palladium(Ⅱ)- Catalyzed Ethylene Polymerization,Organometallics,1997,16,1514-1516.
[3]Gibson,V.C.,Maddox,P.J.,Newton,C.,Redshaw,C.,Solan,G.,White,A.J.P.,Williams,D.J.,Maddox,P.J.,Chromium(Ⅲ) complexes bearing N,N-chelate ligands as ethene polymerization catalysts,Chem.Commun.,1998,1651-1652.
[4]Odile,D.C.,Blanca,M.V.,Didier,B.,Controlled Ring-Opening Polymerization of Lactide and Glycolide.Chem.Rev.2004,104,6147-6176.
[5]McCarthy,P.J.,Hovry,R.J.,Inner Complex Chelates I.Analogs of Bisacetylacetoneethylenediimine and its Metal Chelates,J.Am.Chem.Soc.,1955,77,5820-5824.
[6]Schauzer,G.N.,Organocobalt Chemistry of Vitamin B12 Model Compounds,Acc.Chem.Res.,1968,1,197-201.
[7]Schauzer,G.N.,New Development in the Field of Vitamin B12,Angew.Chem.Int.ed.Engl.,1976,15,417-421.
[8]Dowd,P.,Trivedi,B.K.,Vitamin B12 Model Studies,J.Am.Chem.Soc.,1976,98,7875-7879.
[9]Chauzer,G.N.,New Development in the Field of Vitamin B12,Angew.Chem.Int.ed.Engl.,1977,16,233-235.
[10]Mansury,D.,Cytochtome P-450 and Synthetic Models,Pure and Appl.Chem.,1987, 59, 759-762.
[11] Rieth, L. R., Coates, G. W., Single-Site β -Diiminate Zinc Catalysts for the Ring-Opening Polymerization of β -Butyrolactone and β -Valerolactone to Poly(3-hydroxyalkanoates), J.Am. Chem. Soc, 2002, 124, 15239-15248.
[12] Chamberlain, B. W., Coates, G W., Polymerization of Lactide with Zinc and Magnesium β -Diiminate Complexes: Stereocontrol and Mechanism, J. Am. Chem. Soc, 2001, 123, 3229-3238.
[13] (a) Darensbourg, D. J., Holtcamp, M. W., Catalytic Activity of Zinc(II) Phenoxides Which Possess Readily Accessible Coordination Sites. Copolymerization and Terpolymerization of Epoxides and Carbon Dioxide. Macromolecules, 1995, 28,7577. (b) Darensbourg, D. J., Holtcamp, M. W., Catalysts for the reactions of epoxides and carbon dioxide.Coord. Chem. Rev. 1996,153, 155. (c) Super, M. S.,Berluche, E., Costello, C. A., Beckman, E. J.Polym. Mat. Sci. Eng. Prepr. 1996, 74, 430. (d) Super, M. S., Beckman, E.J., Macromol. Symp. 1998, 127, 89. (e) Cheng, M., Lobkovsky, E. B.,Coates,G. W., Catalytic Reactions Involving C_1 Feedstocks: New High-Activity Zn(II)-Based Catalysts for the Alternating Copolymerization of Carbon Dioxide and Epoxides. J. Am. Chem. Soc. 1998, 120, 11018. (f) Beckman, E. Science 1999,283, 946. (g) Nazaki, K., Nakano, K., Hiyama, T. A Highly Enantio-Selective Hexitol Nucleic Acid Template for Nonenzymatic Oligoguanylate Synthesis. J. Am. Chem. Soc. 1999,121, 1108. (h) Cheng, M., Darling, N. A., Lobkovsky, E. B., Coates, G.W., Enantiomerically-enriched organic reagents via polymer synthesis: enantioselective copolymerization of cycloalkene oxides and CO2 using homogeneous, zinc-based catalysts.J. Chem. Soc, Chem. Commun. 2000, 20,2007-2008.
[14] Cheng, M., Moore, D. R., Reczek, J. J., Chamberlain, B. M., Lobkovsky, E. B., Coate, G. W., Single-Site P-Diiminate Zinc Catalysts for the Alternating Copolymerization of CO2 and Epoxides: Catalyst Synthesis and Unprecedented Polymerization Activity, J. Am. Chem. Soc, 2001,123, 8738-8749.
[15] Darensbourg, D. J., Phelps, A. L., Copolymerization of CO_2 and Epoxides Catalyzed by Metal Salen Complexes,Acc.Chem.Res.,2004,37,836-844.
[16]Coates,G.W.and Moore,D.R.,Discrete Metal-Based Catalysts for the Copolymerization of CO_2 and Epoxides:Discovery,Reactivity,Optimization,and Mechanism,Angew.Chem.Int.ed.Engl.,2004,43,6618-6625.
[2]Zeise,W.C.,Ann.Phys.,1827,9,632-635.
[3]张立新.黄祖恩,周锡庚,马怀柱.稀土金属有机化学的发展概况.上海化工.1998,6,37-39.
[4]白峰,李弘.胍在不对称合成中的应用.有机化学,2004,24,1532-1541.
[5]Ohtani,I.;Kusumi,T.;Kajusawa,H.;Kashman,Y.;and Shulamit,H.,Structure and Chemical Properties of Ptilomycalin A,J Am Chem Soc,1992,114,8472-8479.
[6]宋伟,陆晓峰,陆国元.间二苄胍衍生物的合成.高等学校化学学报,2006,27,460-463.
[7]Bailey,P.J.;Pace,S.,The coordination chemistry of guanidines and guanidinates.,Coord Chem Rev,2001,214,91-141.
[8] (1)Gobel, M.; Klapotke, T. M., et al. First structural characterization of guanidine, HN=C(NH_2)(2), Chem Commun., 2007, (30):3180-3182.
[9] Sotome, Y.; Takemura, N., et al. Organocatalytic asymmetric nitroaldol reaction: Cooperative effects of guanidine and thiourea functional groups, Chemistry-An Asian Journal, 2007,2, 1150-1160.
[10] Rodriguez, F.; Rozas, I., et al. Guanidine and 2-aminoimidazoline aromatic derivatives as alpha(2)-Adrenoceptor antagonists, 1:Toward new antidepressants with heteroatomic linkers, J Med Chem, 2007, 50,4516-4527.
[11] Maiti, K. K.; Lee, W. S., et al. Guanidine-containing molecular transporters: Sorbitol-based transporters show high intracellular selectivity toward mitochondria, Angew Chem Int Ed, 2007, 46, 5880-5884.
[12] Gerard, B.; Denis, G; Pierre, S. J., et al. Pentaalkylguanidines as etherification and esterification catalysts, Tetrahedron, 1990, 46, 1839-1848.
[13] Zhang, W. X.; Nishiura, M., et al. Catalytic addition of amine N-H bonds to carbodiimides by half-sandwich rare-earth metal complexes: Efficient synthesis of substituted Guanidines through amine protonolysis of rare-earth metal guanidinates, Chem EurJ, 2007,13, 4037-4051.
[14] Parks, J. E., Holm, R. H., Synthesis, solution stereochemistry, and electron delocalization properties of bis(β-iminoamino)nickel(II) complexes, Inorg. Chem., 1968, 7, 1408-1416.
[15] Hichcock, P. B., Lappert, M. F., Liu, D. S., (a) Transformation of the bis (trime thylsilyl)methyl into a β-diketinimato ligand; the X-ray structure of [Li(L'L')]_2, SnCl(Me)_2(L'L') and SnCl(Me)_2(L'L'), [L'L'=N(R)C(Ph)C(H)C(Ph)- LL=N(H)C(Ph) C(H)C(Ph)NH,R=SiMe_3],J.Chem.Soc.,Chem.Commun.,1994, 1699-1700. (b) Transformation of the bis -(trimethylsilyl)methyl into aza-allyl and β-diketinimato ligands; the X-ray structures of [Li{N(R)C(Bu~t)CH(R)}]_2 and [Zr{N(R)C (Bu~t)CH C(Ph)N(R)}Cl_3] (R=SiMe_3), J. Chem. Soc, Chem. Commun., 1994, 2637- 2638
[16]Ziniuk,Z.,Goldberg I.,Kol M.,Zirconium complexes of chelating dianionic bis -(pentafluorophenylamido) ligands:synthesis,structure and ethylene polymerisation activity,Inorg.Chem.Commun.,1999,2,549-551.
[17]Liang,L.-C.,Schrock,R.R.,Davis,W.M.,McConvelle,D.H.,Synthesis of Group 4Complexes that Contain the Diamidoamine Ligands,[(2,4,6-Me_3C_6H_2NCH_2CH_2)_2NR]_2-([Mes_2N_2NR]~(2-);R=H or CH_3),and Polymerization of 1-Hexene by Activated [Me_2N_2NR]ZrMe_2 Complexes,J.Am.Chem.Soc.,1999,121,5797-5798.
[18]Graf,D.D.,Schrock,R.R.,Daves,W.M.,Stumpf,R.,Synthesis of Zirconium Complexes Containing the Tridentate Diamido Ligands[(t-Bu-d_6-N-o-C_6H_4)_2S]~(2-) and [(i-PrN-o-C_6H_4)_2S]~(2-),Organometallics,1999,18,843-852.
[19]Mack,H.and Eisen,M.S.,Synthesis,characterization and reactivity of amido titanium and zirconium complexes,J.Organomet.Chem.,1996,525,81-87.
[20]Tshuva,E.Y.,Goldberg,I.,Kol,M.,Goldschmidt,Z.,Zirconium Complexes of Amine -Bis(phenolate) Ligands as Catalysts for 1-Hexene Polymerization:Peripheral Structural Parameters Strongly Affect Reactivity,Organometallics,2001,20,3017-3028.
[21]Tshuva,E.Y.,Goldberg,I.and Kol,M.,Isospecific Living Polymerization of 1-Hexene by a Readily Available Nonmetallocene C_2-Symmetrical Zirconium Catalyst,J.Am.Chem.Soc.,2000,122,10706-10707.
[22]Hichcock,P.B.,Lappert,M.F.,Liu,D.S.,(a) Transformation of the bis(trimethylsilyi)methyl into a β-diketinimato ligand;the X-ray structure of [Li(L'L')]_2,SnCl(Me)_2(L'L') and SnCl(Me)_2(L'L'),[L'L'=N(R)C(Ph)C(H)C(Ph)NR,LL=N(H)C(Ph)C(H)C(Ph)NH,R=SiMe_3),J.Chem.Soc.,Chem.Commun.,1994,1699-1700;
(b) Transformation of the bis -(trimethylsilyl)methyl into aza-allyl and β-diketinimato ligands;the X-ray structures of[Li{N(R)C(Bu~t)CH(R)}]_2 and [Zr{N(R)C(Bu~t)CHC(Ph)N(R)}Cl_3](R=SiMe_3),J.Chem.Soe.,Chem.Commun.1994,2637-2638.
[23]Paulmier,C.,Mollier,Y.,Lozac'h,N.,Bull.Soc.Chim.Fr.,1965,2463.
[24]Kulichenlo,A.V.,Kurbatov,V.P.,Kukharicheva,E.S.,Osipov,O.A.,J.Gen.Chem.,USSR,1985,55,612.
[25]Maraval,A.,Arquier,D.,Igau,A.,Coppel,Y.,Donnadieu,B.,Majoral,J.-P.,Malonodinitrile CH_2(CN)_2 as Synthon for the Preparation of Unprecedented N-Metalla- and N-Phosphino-β-diimine Ligands,Organometallics,2001,20,1716-1718.
[26]Fustero,S.,de la Torre,M.G.,Pina,B.,Fuentes,A.S.,New Strategies for the Synthesis of Fluorinated Vinylogous Amidines and β-Enamino Ketones,J.Org.Chem.,1999,64,5551-5556.
[27]Yokota,S.,Tachi,Y.,Nishiwaki,N.,Ariga,M.,Itoh,S.,A New β-Diketiminate Ligand Carrying a Functional Group on the Carbon Framework.Synthesis and Characterization of a Linear Polymeric Copper(Ⅰ) Complex,Inorg.Chem.,2001,40,5316-5317.
[28]Bradley,D.C.,Thomas,I.M.,Proc.Chem.Soc.,1959,225-226.
[29]Feldman,J.,Mclain,S.J.,Parthasarathy,A.,Marshall,W.J.,Calabrese,C.J.,Arthur,S.D.,Electrophilic Metal Precursors and a β-Diimine Ligand for Nickel(Ⅱ)- and Palladium(Ⅱ)- Catalyzed Ethylene Polymerization,Organometallics,1997,16,1514.
[30]Cui,C.,Roesky,H.W.,Schmidt,H.-G.,Moltemeyer,M.,Hao,H.,Cimpoesu,F.,[HC{(CMe)(NAr)}_2]Al[(NSiMe_3)_2N_2](Ar=2,6-iPr_2C_6H_3):The First Five-Membered AlN_4 Ring System,Angew.Chem.,Int.Ed,2000,39,4531-4533.
[31]Hardman,N.J.,Eichler,B.E.,Power,P.P.,Synthesis and characterization of the monomer Ga{(NDippCMe)_2CH}(Dipp=C_6H_3Pr_2~i-2,6):a low valent gallium(ⅰ) carbene analogue,Chem.Commun.,2000,1991-1992.
[32]Stender,M.,Phillips,A.D.,Power,P.P.,Characterization and Bonding of the Cation [Ge{N(C_6H_3-2,6-i-Pr_2)CMe}_2CH]~+:Comparison with the Isoelectronic Ga{N(C_6H_3-2,6-i-Pr_2)-CMe}_2CH,Inorg.Chem.,2001,40,5314-5315.
[33]Fekl,U.,Kaminsky,W.,Goldberg,K.I.,A Stable Five-Coordinate Platinum(Ⅳ) Alkyl Complex,J..Am.Chem.Soc.,2001,123,6423-6424.
[34]Gibson,V.C.,Maddox,P.J.,Newton,C.,Redshaw,C.,Solan,G.,White,A.J.P.,Williams,D.J.,Maddox,P.J.,Chromium(Ⅲ) complexes bearing N,N-chelate ligands as ethene polymerization catalysts,Chem.Commun.,1998,1651-1652.
[35]Holland,P.L.,Tolman,W.B.,A Structural Model of the Type 1 Copper Protein Active Site:N2S(thiolate)S(thioether) Ligation in a Cu(Ⅱ) Complex,J.Am.Chem.2000,122,6331-6332.
[36]Chamberlain,B.M.,Cheng,M.,Moore,D.R.,Ovitt,T.M.,Lobkovsky,E.B.,Coate,G.W.,Polymerization of Lactide with Zinc and Magnesium β-Diiminate Complexes:Stereocontrol and Mechanism,J.Am.Chem.Soc.,2001,123,3229-3238.
[37]Dove,A.P.,Gibson,V.C.,Marshall,E.L.,White,A.J.P.,Williams,D.J.,A well defined tin(ii) initiator for the living polymerization of lactide,Chem.Commun.,2001,283-284.
[38]Cheng,M.,Moore,D.R.,Reczek,J.J.,Chamberlain,B.M.,Lobkovsky,E.B.,Coate,G.W.,Single-Site β-Diiminate Zinc Catalysts for the Alternating Copolymerization of CO2and Epoxides:Catalyst Synthesis and Unprecedented Polymerization Activity,J.Am.Chem.Soc.,2001,123,8738-8749.
[39]张宗勇,闫玉华.聚乳酸在生物医学领域中的应用,精细与专用化学品,2005,13,7-10.
[40]Das,K.G.,Controlled release technology bioengineering aspects.New York:JohnWiley and Sons,1983.
[41]俞耀庭,张兴栋.生物医用材料,天津:天津大学出版社,2000.181.
[42]牛旭锋,王远亮,罗彦凤,石梁平.内消旋丙交酯及其聚合物的研究进展,高分子材料科学与工程.2005,21,4,34-36.
[43]Williams,C.K.;Brooks,N.R.;Tolman,W.B.,Metalloenzyme inspired dizinc catalyst for the polymerization of lactide,Chem.Commun.,2002,2132-2133.
[44]Wu,J.C.;Yu,T.L.,Recent developments in main group metal complexes catalyzed/initiated polymerization of lactides and related cyclic esters.Coordination Chemistry Reviews.2006,250,602-626.
[45]姚英明,沈琪.二(2,6-二叔丁基-4-甲基苯氧基)钐催化丙交酯开环聚合,应用化学,1998,15,62-64.
[46]崔冬梅,程建华,朱宁,唐涛,陈文启,黄葆同.二价茂稀土配合物催化左旋丙交酯的开环聚合,科学通报,2002,47,418-420.
[47]刘小兰,赵茹,刘晓红,岳俊杰,陈克,缪方明.新型桥连双锌配合物的合成和结构,化学学报,2003,61,578-583.
[48]沈之荃,孙俊全,吴良江,吴兰亭.稀土配位催化合成聚乳酸,化学学报,1990,48:686-689.
[49]袁福根.桥联双金属稀土配合物对丙交酯的催化聚合研究,铁道师范学报,1999,16,4,38-41.
[50]Ford,T.M.;Drysdale N.E.,ACS Polymer Prep,1992,33,463-475.
[51]王小莺,廖凯荣,全大萍,伍青.醇铁化合物引发丙交酯开环聚合机理的研究,中山大学学报(自然科学版),2005,44,42-45.
[52]张杰,胡平,周新林,甘志华.丙交酯的制备及其开环聚合,吉林工业大学学报.1998,28,266-270.
[1]白峰,李弘.胍在不对称合成中的应用.有机化学,2004,24:1532-1541.
[2]宋伟,陆晓峰,陆国元.间二苄胍衍生物的合成.高等学校化学报,2006,27,460-463.
[3]Ohtani,I.;Kusumi,T.;Kajusawa,H.;Kashman,Y.;and Shulamit,H.,Structure and Chemical Properties of Ptilomycalin A,J Am Chem Soc,1992,114,8472-8479.
[4]Gobel,M.;Klapotke,T.M.,et al.First structural characterization of guanidine,HN=C(NH_2)(2),Chem Commun.,2007,(30):3180-3182.
[5]Sotome,Y.;Takemura,N.,et al.Organocatalytic asymmetric nitroaldol reaction:Cooperative effects of guanidine and thiourea functional groups,Chemistry-An Asian Journal,2007,2,1150-1160.
[6]Paul A.Boguszewski,Shahzard S.Rahaman,A Ganesan.Modular three-component solid-phase synthesis of unsymmtrical guanidines via resin capture of carbodiimides.J.Comb.Chem,2004,6(1),32-34.
[7]Christoph W.Zapf,Murray Goodman.Synthesis of 2-amino-4-pyrimidinones from resin-bound guanidines prepared using bis(allyloxycarbonyl)-protected triflylguanidine.J.Org.Chem.,2003,68(26),10092-10097.
[8]Masahiro Terada,Takashi lkehara,Hitoshi Ube.Enantioselective 1,4-addition reactions of diphenyl phosphite to nitroalkenes catalyzed by axially chiral guanidine,J.Am.Chem.Soc,2007,129(46)
[9]Craig A.Miller,Robert A.Batey.Hetero Diels-AIder reactions of nitrosoamidines:an efficient method for the synthesis of functionalized guanidines.Org.Lett.2004,6(5),699-702.
[10]Hao Shen,Zuowei Xie.Titanacarborane amide catalyzed transamination of guanidines.Organometallics 2008,27,2685-2687.
[11]Jing Li,Wan-Yi Jiang,Ke-Li Han.Density functional study on the mechanism of bicyclic guanidine-catalyzed Strecker reaction.J.Org.Chem.2003,68,8786-8789.
[1](a) Edelmann,F.T.,Angew.Chem.Int.Ed,1995,34,2466;
(b) Edelmann,F.T.,Freckmann,D.M.,Schumann,M.H.,Synthesis and Structural Chemistry of Non-Cyclopentadienyl Organolanthanide Complexes,Chem.Rev.,2002,102,1851-1896;
(c) Piers,W.E.,Emslie,D.J.H.,Non-cyclopentadienyl ancillaries in organogroup 3 metal chemistry:a fine balance in ligand design,Coord.Chem.Rev.,2002,233-234,131-155.
[2]Feldman,J.,McLain,S.J.,Parthasarathy,A.,Marshall,W.J.,Calabrese,C.J.,Arthur,S.D.,Electrophilic Metal Precursors and a β-Diimine Ligand for Nickel(Ⅱ)-and Palladium(Ⅱ)- Catalyzed Ethylene Polymerization,Organometallics,1997,16,1514-1516.
[3]Gibson,V.C.,Maddox,P.J.,Newton,C.,Redshaw,C.,Solan,G.,White,A.J.P.,Williams,D.J.,Maddox,P.J.,Chromium(Ⅲ) complexes bearing N,N-chelate ligands as ethene polymerization catalysts,Chem.Commun.,1998,1651-1652.
[4]Odile,D.C.,Blanca,M.V.,Didier,B.,Controlled Ring-Opening Polymerization of Lactide and Glycolide.Chem.Rev.2004,104,6147-6176.
[5]McCarthy,P.J.,Hovry,R.J.,Inner Complex Chelates I.Analogs of Bisacetylacetoneethylenediimine and its Metal Chelates,J.Am.Chem.Soc.,1955,77,5820-5824.
[6]Schauzer,G.N.,Organocobalt Chemistry of Vitamin B12 Model Compounds,Acc.Chem.Res.,1968,1,197-201.
[7]Schauzer,G.N.,New Development in the Field of Vitamin B12,Angew.Chem.Int.ed.Engl.,1976,15,417-421.
[8]Dowd,P.,Trivedi,B.K.,Vitamin B12 Model Studies,J.Am.Chem.Soc.,1976,98,7875-7879.
[9]Chauzer,G.N.,New Development in the Field of Vitamin B12,Angew.Chem.Int.ed.Engl.,1977,16,233-235.
[10]Mansury,D.,Cytochtome P-450 and Synthetic Models,Pure and Appl.Chem.,1987, 59, 759-762.
[11] Rieth, L. R., Coates, G. W., Single-Site β -Diiminate Zinc Catalysts for the Ring-Opening Polymerization of β -Butyrolactone and β -Valerolactone to Poly(3-hydroxyalkanoates), J.Am. Chem. Soc, 2002, 124, 15239-15248.
[12] Chamberlain, B. W., Coates, G W., Polymerization of Lactide with Zinc and Magnesium β -Diiminate Complexes: Stereocontrol and Mechanism, J. Am. Chem. Soc, 2001, 123, 3229-3238.
[13] (a) Darensbourg, D. J., Holtcamp, M. W., Catalytic Activity of Zinc(II) Phenoxides Which Possess Readily Accessible Coordination Sites. Copolymerization and Terpolymerization of Epoxides and Carbon Dioxide. Macromolecules, 1995, 28,7577. (b) Darensbourg, D. J., Holtcamp, M. W., Catalysts for the reactions of epoxides and carbon dioxide.Coord. Chem. Rev. 1996,153, 155. (c) Super, M. S.,Berluche, E., Costello, C. A., Beckman, E. J.Polym. Mat. Sci. Eng. Prepr. 1996, 74, 430. (d) Super, M. S., Beckman, E.J., Macromol. Symp. 1998, 127, 89. (e) Cheng, M., Lobkovsky, E. B.,Coates,G. W., Catalytic Reactions Involving C_1 Feedstocks: New High-Activity Zn(II)-Based Catalysts for the Alternating Copolymerization of Carbon Dioxide and Epoxides. J. Am. Chem. Soc. 1998, 120, 11018. (f) Beckman, E. Science 1999,283, 946. (g) Nazaki, K., Nakano, K., Hiyama, T. A Highly Enantio-Selective Hexitol Nucleic Acid Template for Nonenzymatic Oligoguanylate Synthesis. J. Am. Chem. Soc. 1999,121, 1108. (h) Cheng, M., Darling, N. A., Lobkovsky, E. B., Coates, G.W., Enantiomerically-enriched organic reagents via polymer synthesis: enantioselective copolymerization of cycloalkene oxides and CO2 using homogeneous, zinc-based catalysts.J. Chem. Soc, Chem. Commun. 2000, 20,2007-2008.
[14] Cheng, M., Moore, D. R., Reczek, J. J., Chamberlain, B. M., Lobkovsky, E. B., Coate, G. W., Single-Site P-Diiminate Zinc Catalysts for the Alternating Copolymerization of CO2 and Epoxides: Catalyst Synthesis and Unprecedented Polymerization Activity, J. Am. Chem. Soc, 2001,123, 8738-8749.
[15] Darensbourg, D. J., Phelps, A. L., Copolymerization of CO_2 and Epoxides Catalyzed by Metal Salen Complexes,Acc.Chem.Res.,2004,37,836-844.
[16]Coates,G.W.and Moore,D.R.,Discrete Metal-Based Catalysts for the Copolymerization of CO_2 and Epoxides:Discovery,Reactivity,Optimization,and Mechanism,Angew.Chem.Int.ed.Engl.,2004,43,6618-6625.