N、O-二齿配合物的合成及应用
摘要
金属锌化合物由于其在生命科学、新材料、催化剂等方面的重要作用及其无毒、无污染等特性引起了人们的广泛关注。特别是二价锌配合物所具有的特性,如无色,低成本,低毒等,由其催化所得的聚合物在生物医学领域有很重要的应用,因此,由二价锌配合物引发的丙交酯的聚合反应被广泛研究。丙交酯的开环聚合近年来引起人们越来越多的注意,因为由此所得的聚乳酸易分解并具有生物相容性,而且可以作为一种潜在的新型环境友好型聚酯材料。因此,各国化学工作者研究的热点是在设计合成新型的金属锌有机化合物,寻求更高催化活性及选择性的催化剂。
本论文以上述研究背景为前提,进行了一系列的研究工作。论文主要分为以下四章内容:
第一章为导论,介绍了本论文工作的研究背景,分为四个部分:(1)吡啶基金属有机化合物及其成键模式;(2)含氮、氧原子有机配体的研究及其金属配合物的应用;(3)脒基化合物及合成方法的研究进展;(4)丙交酯开环聚合合成聚乳酸的研究进展。
第二章以2-P比啶醛与α-苯乙胺为母体合成一些桥联化合物,并将它们与ZnEt_2、AlMe_3反应合成一系列金属配合物,然后通过NMR、X-Ray单晶衍射等手段对其进行了结构表征。
第三章分别以N,N-二甲基邻甲苯胺和N,N-二甲苯胺为起始原料合成一系列含氮、氧原子的配体化合物,并用NMR对这些化合物进行分析表征;将合成的配体化合物分别与ZnEt_2、AlMe_3反应得到一系列金属锌、铝的氮、氧-二齿配合物,并通过用NMR和X-射线单晶衍射等手段对其进行了结构表征。
第四章主要将上述得到的金属锌、铝化合物用于催化丙交脂开环聚合反应,通过用NMR、凝胶色谱分析和熔点测定等手段对合成的聚乳酸进行了结构和性质表征,并对催化反应的机理进行研究。
Zinc metal compounds,playing important roles in life science,new materials,catalysts and non-toxic,non-polluting characteristics have attracted extensive attentions.In particularly,polymerization of lactide initiated by Zn(Ⅱ) complexes has been investigated vastly because of their unique features,such as lack of color,low cost,and low toxicity which are important in biomedical applications of the polymer.The ring-opening polymerization (ROP) of lactide(LA) has received increasing attention recently because the resultant polylactide(PLA) is easily degradable and biocompatible and has potential as a new environmentally-friendly thermoplastic.Hence,the design and synthesis of new organic zinc metal compounds as initiatores for ring-opening polymerization of lactide to seek higher catalytic activity and selectivity is one of the hottest topics for chemists.
The details of this paper are divided into four chapters,the contents as follows:
Chapter 1.Introduction to the research background of this thesis:(1) The synthesis and bonding modes of organometallics complexes with substituted pyridine;(2) The study and applications of organic ligands with nitrogen and oxygen atoms and their metal complexes;(3) Research progress of amidine compounds and their synthetic methods;(4) Research developments of PLA.
Chapter 2.Some bridged ligands were prepared from pyridine-2-carboxaldehyde and 1-phenylethanamine,which were used to synthesize a series of organometallic complexes by reacting with ZnEt_2 or AlMe_3.
Chapter 3.Some new N,O-bidentate ligands were prepared from N,N-dimethyl-o-toluidine and N,N-dimethylbenzen-amine and their organometallic complexes were synthesized from the reaction of relevant ligand and ZnEt_2 or AlMe_3.All the organometallic compounds were characterized by NMR and X-my diffraction analysis.
Chapter 4.The organometallic complexes synthesized in chapter 3 used as initiator for catalytic the ring-opening polymerization(ROP) of lactide were stduied.The Polylactide were structurally characterized by NMR,Gel Permeation Chromatography(GPC) and Melting point.
本论文以上述研究背景为前提,进行了一系列的研究工作。论文主要分为以下四章内容:
第一章为导论,介绍了本论文工作的研究背景,分为四个部分:(1)吡啶基金属有机化合物及其成键模式;(2)含氮、氧原子有机配体的研究及其金属配合物的应用;(3)脒基化合物及合成方法的研究进展;(4)丙交酯开环聚合合成聚乳酸的研究进展。
第二章以2-P比啶醛与α-苯乙胺为母体合成一些桥联化合物,并将它们与ZnEt_2、AlMe_3反应合成一系列金属配合物,然后通过NMR、X-Ray单晶衍射等手段对其进行了结构表征。
第三章分别以N,N-二甲基邻甲苯胺和N,N-二甲苯胺为起始原料合成一系列含氮、氧原子的配体化合物,并用NMR对这些化合物进行分析表征;将合成的配体化合物分别与ZnEt_2、AlMe_3反应得到一系列金属锌、铝的氮、氧-二齿配合物,并通过用NMR和X-射线单晶衍射等手段对其进行了结构表征。
第四章主要将上述得到的金属锌、铝化合物用于催化丙交脂开环聚合反应,通过用NMR、凝胶色谱分析和熔点测定等手段对合成的聚乳酸进行了结构和性质表征,并对催化反应的机理进行研究。
Zinc metal compounds,playing important roles in life science,new materials,catalysts and non-toxic,non-polluting characteristics have attracted extensive attentions.In particularly,polymerization of lactide initiated by Zn(Ⅱ) complexes has been investigated vastly because of their unique features,such as lack of color,low cost,and low toxicity which are important in biomedical applications of the polymer.The ring-opening polymerization (ROP) of lactide(LA) has received increasing attention recently because the resultant polylactide(PLA) is easily degradable and biocompatible and has potential as a new environmentally-friendly thermoplastic.Hence,the design and synthesis of new organic zinc metal compounds as initiatores for ring-opening polymerization of lactide to seek higher catalytic activity and selectivity is one of the hottest topics for chemists.
The details of this paper are divided into four chapters,the contents as follows:
Chapter 1.Introduction to the research background of this thesis:(1) The synthesis and bonding modes of organometallics complexes with substituted pyridine;(2) The study and applications of organic ligands with nitrogen and oxygen atoms and their metal complexes;(3) Research progress of amidine compounds and their synthetic methods;(4) Research developments of PLA.
Chapter 2.Some bridged ligands were prepared from pyridine-2-carboxaldehyde and 1-phenylethanamine,which were used to synthesize a series of organometallic complexes by reacting with ZnEt_2 or AlMe_3.
Chapter 3.Some new N,O-bidentate ligands were prepared from N,N-dimethyl-o-toluidine and N,N-dimethylbenzen-amine and their organometallic complexes were synthesized from the reaction of relevant ligand and ZnEt_2 or AlMe_3.All the organometallic compounds were characterized by NMR and X-my diffraction analysis.
Chapter 4.The organometallic complexes synthesized in chapter 3 used as initiator for catalytic the ring-opening polymerization(ROP) of lactide were stduied.The Polylactide were structurally characterized by NMR,Gel Permeation Chromatography(GPC) and Melting point.
引文
[1]21世纪中国有机化学发展战略研讨会纪要,2001年4月,上海
[2]Jr.John Boor著,孙伯庆,张玉岜,栾瑛洁等译.齐格勒-纳塔催化剂和聚合[M].北京:化学工业出版社,1986.
[3]黄葆同,沈之荃等.烯烃双烯烃配位聚合进展[M].北京:科学出版社,1998.
[4]J.A.Ewen,Mechanisms of Stereochemical Control in Propylene Polymerizations with Soluble Group 4B Metallocene / Methylalumoxane Catalysts,J.Am.Chem.Soc.,1984,106,6355-6364.
[5]L.K.Johnson;M.F.Brookhart;C.M.Killian,New Pd(Ⅱ)-and Ni(Ⅱ)-Based Catalysts for Polynerization of Ethylene and α-Olefins,J.Am.Chem Soc.,1995,117,6414-6415.
[6]C.M.Killian;L.K.Johnson,et al.α-Olefins and Olefin Polymers and Processes Therefore[P].WO 9623010.1996-08-01.
[11]Caro,C.F.;Lappert,P.G.;Coordin.,M.F.;Merle,Review of Metal 1-azaallyl Complexes,Chem.Rev.,2001,219,605-663.
[12]Chakravarty,A.R.;Shamshoum,E.S.and Cotton,F.A.,2-Anilinopyridine complexes of dimolybdenum(Ⅱ) and ditungsten(Ⅱ),Inorg.Chem.,1984,23,4216-4221.
[13]Barr,D.;Mulvey,R.E.;Clegg,W.and Snaaith,R.,The structural isomers of {[ph(2-pyridyl)NLi].[O=P(NMe_2)_3]}_2:dimeric species with alternative central(LiN)_2and(LiO)_2 rings,the latter involving unprecedented neutral bridging oxygen ligands,J.Chem.Soc.,Chem.,Commun.,1984,700-703.
[14]Leskel(a|¨),M.and Polamo,M.,Syntheses and crystal structures of phenyl(2-pyridyl)-amido complexes of zirconium(Ⅳ),tantalum(Ⅴ) and niobium(Ⅴ),J.Chem.Soc.,Dalton Trans.,1996,4345-4246.
[15]Cotton,F.A.;Clerac,R.;Dunbar,K.R.;Pascual,I.;Murillo,C.A.and Wang,X.,Further Study of the Linear Trinickel(Ⅱ) Complex of Dipyridylamide,Inorg.Chem.,1999,38,2655-2657.
[16]Spannenberg,A.;Kempe,R.and Arndt,P.,Yttrate-Mediated Ligand Transfer and Direct Synthesis as a Route to Amidopalladium Complexes,Angew Chem.lnt.Ed.,1998,37,832-835.
[17]Edema.J.J.H.;Gambarotta,S.;Meetsma,A.;Veldman,N.and Spek,S.L.,Synthesis and structural features of novel vanadium(Ⅱ) amides,Inorg.Chem.,1991,30,2062-2066.
[18]Kempe,R.,Highlights der Renaissance der Amidometallchemie,Angew.Chem.,2000, 112, 478-504.
[19] Sekutowski, J. C.; Niswander, R. H.; Cotton, F. A., Homologous chromium, molybdenum, and tungsten compounds with very short quadruple bonds, Inorg.Chem., 1978,77,3541-3545.
[20] Lu, J. Y.; Wang, R. J.; Cabrera, B. R., Chemical Rearrangement under Hydrothermal Conditions: Formation of Polymeric Chains (CuX)2(dpiz) and (CuX)3(dpiz) (X =Cl, Br; dpiz=Dipyridot[1,2-a:2',3'-d]imidazole), Inorg. Chem., 1998, 37, 4480-4481.
[21] Clerac, R.; Cotton, F. A.; Dunbar, K. R.; et al, A New Linear Tricobalt Compound with Di(2-pyridyl)amide (dpa) Ligands: Two-Step Spin Crossover of [Co3(dpa)4C12][BF4],J. Am. Chem. Soc, 2000,122,2272-2278.
[22] Lee, C. F.; Chin, K. F.; Peng, S. M.; et al, A luminescent tetrameric zinc(II) complex containing the 7-azaindolate ligand. Photophysical properties and crystal structure, J.Chem. Soc, Dalton Trans., 1993,467-469.
[23] James, B.; Melvyn, K., The coordination chemistry of the amidine ligand, Coord.Chem. Rev., 1994,133,219
[24] Laurence, B. M., Lappert, M. F. and Severn, J. R., The Chemistry of (?)-Diketiminato-metal Complexes, Chem. Rev. 2002, 702, 3031-3065
[25] Ejfler, J.; Szafert, S.; Mierzwicki, K.; et al, Homo- and heteroleptic zinc aminophenolates as initiators for lactide polymerization, J. Chem. Soc, Dalton Trans., 2008, 6556-6562.
[26] Chen, H. Y.; Lin C. C; Tang, H. Y., Ring-Opening Polymerization of Lactides Initiated by Zinc Alkoxides Derived from NNO-Tridentate Ligands,Macromolecules, 2006, 39, 3745-3752
[27] Jolanta, E.; Michai, K.; Lucjan B.; et al, Highly efficient magnesium initiators for lactide polymerization, DaltonTrans, 2005, 2047-2050
[28] Fredy Speiser; Lucien Saussine; Pieere Braunstein, Dinuclear nickel complexes with bidentate N,0 ligands: synthesis, structure, and catalytic oligomerization of ethylene,Inorg. Chem., 2004, 43, 4234-4240.
[29] (a)Younkin, T. R.; Connor, E. F.; Henderson, J. I.; et al, Science 2000, 288,1750-1751.
(b)Wang, C.; Friedrich, S.; Younkin, T. R.; et al, Organometallics, 1998,17,3149-3151
[30](a)Hicks,F.A.;Brookhart,M.;Jenkins,J.C.,Organometallics,2003,22,3533-3545.
(b) Jenkins,J.C.;Brookhart,M.Organometallics,2003,22,250-256.
[31](a)Qian,Y.;Zhao,W.,J.Inorg.Chem.Commun.,2004,7,459-461.
(b) Sun,W.H.;Zhang,W.;Gao,T.;et al,J.Organomet.Chem.,2004,43,869-873.
[32]Lee,W.S.;Leung,H.K.;Cheng,L.S.;et al,Inorganica Chimica Acta,2004,357,4389-4395
[33]Herrmann,W.A.;Haider,J.J.;Fridgen,J.;et al,d.Organomet.Chem.,2000,603,69-79
[34]Yolanda Perez;Sonia Morante-Zarcero;Isabel Sierra;et al,Inorganica Chimica Acta,2007,360,607-618
[35]Usui,H.;Watanable,Y.;Kanqo,M.J.,Heterocycl.Chem.,1993,30(2),551
[36]Dagorne,S.;Guzei,I.A.;Coles,M.P.;et al,J.Am.Chem.Soc.,2000,122,274;
[37]Dagorne,S.;Jordan,R.F.;Young,V.G.,Organometallics,1999,18,4619
[38]Coles,M.P.;Swenson,D.C.;Jordan,R.F.;et al,Organometallics,1998,17,4042
[39]Coles,M.P.;Swenson,D.C.;Jordan,R.F.;et al,Organometallics,1997,16,5183
[40]Talarico,G.;Budzelaar,P.H.M.;Organometallics,2000,19,5691
[41]Rillich,M;Komber,H.;Boechme,F.;Poiym.Bull(Berlin),1993,31(4),381[42]徐振元,刘毅锋,严巍等.浙江化工,1988,19(6),1
[43]Van,V.P.I.;Van,K.G.;Vcieze,K.J.,Organomet.Chem.,1979,179(1),89
[44]Sanzhiafiapor,D.B.;Tsyganov,A.D.;Doroshenko,Y.E.;et al.,SU 1,736,978
[45]Knyaztva,V.F.;Granik,V.G.;Khim,F.Zh.,1981,15(5),44
[46]Gupten,J.T.;Idoux,J.P.;Leonard,R.;et al.,Synth.Common.,1983,13(13),1083
[47]Basink,V.A.,Oaigins Life Evol.Biosphere,1992,22(6),333
[48]Xia,A.i.;Hani,M.E.;Mary J.H.;et al,Synthesis,structure,and properties of magnesium complexes containing cyclopentadienyl and amidinate ligand sets,J.Organomet.Chem.,2003,682,224-232
[49]李瑞.21世纪绿色功能材料-聚乳酸,福建师范大学福清分校学报,2005,2,53-55
[50]朱久进,王远亮.丙交酯的合成与聚合,化工新型材料,2005,33,19-21.
[51]高俊,江志荣.丙交酯开环法合成聚乳酸工艺探讨,合成技术及应用,2005,20,6-8
[52]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
[53]Das,K.G.,Controlled release technology bioengineering aspects.New York:JohnWiley and Sons,1983
[54]俞耀庭,张兴栋.生物医用材料,天津:天津大学出版社,2000.181
[55]牛旭锋,罗彦凤,王远亮,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
[56](a)Chisholm,M.H.;Gallucci,J.,Lactide polymerization by well-difined calcium coordination complexes:comparisons with related magnesium and zinc chemistry,Chem.Commum.,2003,48-49
[57]Chamberlain,B.M.;Cheng,M.;Moore,D.R.;et al,Polymerization of Lactide with zinc and magnesium β-diiminate complexes:stereocontrol and mechanism,J.Am.Chem.Soc.,2001,123,3229-3231
[58]Shueh,M.L.;Lin,C.C.;Wang,Y.S.,Reactions of 2,2'-Methyl-enebis (4-chloro-6-isopropyl-3-methylphenol) and 2,2'-Ethylidenebis(4,6-di-tertbutylphenol)with MgnBu_2:Efficient catalysts for ring-opening polymerization of caprolactone and L-Lactide,Macromolecules,2004,37,5155-5162
[59]Chisholm,M.H.;Zhen,H.S.;Gallucci,J.C.,Three-coordinate zinc amide and phenoxide complexes supported by a bulky Schiff base ligand,Inorg.Chem.,2001,40,5051-5054
[60]Hitchcock,P.B.;Hill,M.S.,Synthesis of C_2 and C_8 symmetric zinc complexes supported by bis(phosphinimino)methyl ligands and their use in ring-opening polymerization catalysis,J.Chem.Soc.,Dalton Trans.,2002,4694-4702
[61]Williams,C.K.;Tolman,W.B.;Brooks,N.R.,Metalloenzyme inspired dizinc catalyst for the polymerization of lactide,Chem.Commun.,2002,2132-2133.
[62]Yu,T.L.;Wu,J.C.,Recent developments in main group metal complexes catalyzed/initiated polymerization of lactides and related cyclic esters.Coordination Chemistry Reviews.2006,250,602-626
[63]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
[64]崔冬梅,朱宁,程建华,陈文启,唐涛,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.
[65]刘小兰,赵茹,刘晓红,岳俊杰,缪方明,陈克.新型桥连双锌配合物的合成和结构,化学学报,2003,61,578-583
[66]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
[67]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
[68]Dubois,P.;Jacobs,C.;Jerome,R.;et al,Macromolecular engineering of polylactones and polylactides.Mechanism and kinetics of lactide homopolymerization by aluminum isopropoxide,Macromolecules,1991,24,2266-2270
[69]甘志华,张杰,胡平,周新林.丙交酯的制备及其开环聚合,吉林工业大学学报1998,28,266-270
[70]Ford,T.M.;Drysdale N.E.,ACS Polymer Prep,1992,33,463-475
[71]王小莺,廖凯荣,伍青,全大萍.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(自然科学皈),2005,44,42-45
[72]廖凯荣,王小莺,伍青,全大萍,乙酰丙酮铁催化丙交酯开环聚合的研究,高分子学报,2005,1,113-118
[73]Janeczek,H.;Ddbrzynski,P.;Kasperczyk,J.;et al.Synthesis of biodegradable glycolidegradable glycolide/L-Lactide copolymers using iron compounds as initiators,Polymer,2002,43:2595-2600
[74]Hillmyer,M.A.;Monnier,S.M.;O'Keefe,B.J.;et al.Rapid and controlled polymerization of lactide by structurally characterized ferric alkoxide,J Am Chem Soc,2001,123:339-340
[75]Wardla,W.W.;Multani,R.K.;Bradley,D.C.,Structural chemidtry of the alkoxides (X).Primary alkoxides of tervalent iron,J Chem Soc,1958,126-129
[1]Ziegler,K.,Breil,H.,Martion,H.,DBP973626,1953,11,17.
[2]Natta,G.,Pino,P.,Mazzati,G.,US.Patent 3715344,Ital Priority,1954,6,8.
[3]Sinn,H.;Woldt,R.;Kaminsky,W.;Vollmer,H.J.,"Living Polymers" on Polymerization with Extremely Productive Ziegler Catalysts.,Angew.Chem.,Int.Ed.,1980,19,390-392.
[4]Johnson,L.K.;Brookhart,M.;Killian,C.M.,New Pd(Ⅱ) and Ni(Ⅱ) Based Catalysts for Polymerization of Ethylene and.alpha.-Olefins,J.Am.Chem.Soc.,1995,117,6414-6415.
[5]Bennett,A.M.A.;Small,B.L.;Brookhart,M.,Highly Active Iron and Cobalt Catalysts for the Polymerization of Ethylene,J.Am.Chem.Soc.,1998,120,4049-4051.
[6]Britovsek,G.J.P.;Gibson,V.C.;Kimberley,B.S.;et al,Novel olefin polymerization catalysts based on iron and cobalt,Chem.Commun.,1998,7,849-851.
[7]Coles,M.P.,Application of neutral amidines and guanidines in coordination chemistry,Dalton Trans.,2006,985-1001
[8]James,B.;Melvyn,K.,The coordination chemistry of the amidine ligand,Coord.Chem.Rev.,1994,133,219
[9]Pace,S.;Bailey,P.J.,The coordination chemistry of guanidines and guanidinates,Coord.Chem.Rev.,2001,214,91
[10]K(o|¨)hn,U.;G(u|¨)nther,W.;G(o|¨)rls,H.;et al,Preparation of chiral thioureas,ureas and guanidines from(S)-2-(N,N-dialkylaminomethyl)pyrrolidines,Tetrahedron:Asymmetry,2004,15,1419-1426
[11]Xia,A.B.;Hani M.El-K.;Mary J.H.;et al,Synthesis,structure,and properties of magnesium complexes containing cyclopentadienyl and amidinate ligand sets,J.Organomet.Chem.,2003,682,224-232
[12] (a) S. Dagorne; I.A. Guzei; M.P. Coles; et al,J. Am.Chem. Soc, 2000,122, 274;
(b) S.Dagorne; V.G. Young; R.F. Jordan, Organometallics, 1999, 18, 4619;
(c) D.C.Swenson; M.P. Coles; V.G. Young; R.F. Jordan, Organometallics, 1998, 17, 4042;
(d) M.P. Coles; D.C. Swenson; R.F. Jordan; et al, Organometallics, 1997,16, 5183;
(e) P.H.M. Budzelaar; G. Talarico, Organometallics, 2000,19, 5691.
[13] (a) V. Volkis; E. Nelkenbaum; A. Lisovskii; et al, J. Am. Chem. Soc., 2003, 125,2179;
(b) S.K. Spitzmesser; V.C. Gibson, Chem. Rev., 2003, 103, 283;
(c) R.J.Keaton; L.A. Koterwas; J.C. Fettinger; et al, J. Am. Chem. Soc., 2002,124, 5932;
(d)T.Y. Meyer; J.M. Decker; S.J. Geib, Organometallics, 1999,18, 4417.
[14] J. Barker; N.C. Blacker; P.R. Phillips; et al, J. Chem. Soc. Dalton Trans. 1996,431.
[15] Mansfield, N. E.; Grundy J.; Coles M. P.; et al, A Conformational Study of Phospha(III)- and Phospha(V)-guanidine Compounds, J. Am. Chem. Soc., 2006, 128,13879-13893
[16] Cole, M. L.; Junk, P. C.;Louis, L. M., Synthesis and structural characterisation of some novel lithium and sodium N,N_-di(para-tolyl)formamidinate complexes, J.Chem. Soc, Dalton Trans., 2002, 3906-3914
[17] Dagorne, S.; Guzei, I. A.; Coles, M. P.; et al, Synthesis and Structures of Cationic Aluminum and Gallium Amidinate Complexes, J. Am. Chem. Soc. 2000, 122,274-289
[18] Andrews, P. C; Brym M.; Jones, C.; et al, Inorganica Chimica Acta, 2006, 359,355-363
[19] Mansfield, N. E.; Coles, M. P.; Avent, A. G.; et al, Coordination Chemistry of Isomeric Mixtures of Linked Di(phosphaguanidine) Compounds: A Spectroscopic and Crystallographic Study, Organometallics, 2006,25, 2470-2474
[1]Wu,J.C.;Yu,T.L.;Chen,C.T.;et al,Recent developments in main group metal complexes catalyzed/initiated polymerization of lactides and related cyclic esters,Coordin.Chem.Rev.,2006,250,602-626
[2](a) Gallucci,J.;Chisholm,M.H.,Lactide polymerization by well-difined calcium coordination complexes:comparisons with related magnesium and zinc chemistry,Chem.Commum.,2003,48-49
(b)Chisholm,M.H.;Eilerts,N.W.;Huffman,J.C.;et al,Molecular design of single-site metal alkoxide catalyst precursors for ring-opening polymerization reactions leading to polyoxygenates.1.Polylactide formation by achiral and chiral magnesium and zinc alkoxides,(η~3-L)MOR,where L=Trispyrazolyl-and Trisindazolylborate ligands,J.Am.Chem.Soc.,2000,122,11845-11854
[3] (a)Chamberlain, B. M.; Cheng, M.; Moore, D. R.; et al, Polymerization of Lactide with zinc and magnesium P-diiminate complexes: stereocontrol and mechanism, J. Am.Chem. Soc., 2001,123, 3229-3231
(b)Hormnirun,P.; Marshall, E. L.; Gibson,V. C.; et al, Remarkable Stereoconteol in Polymerization of Racemic Lactide Using Aluminum Initiators Supported by Tetradentate Aminophenoxide Ligands, J. Am. Chem. Soc, 2004,126,2688-2689
[4] Lin, C. C; Shueh, M. L.; Wang, Y. S., Reactions of 2,2'-Methylenebis (4-chloro-6-isopropyl-3-methylphenol) and 2,2'-Ethylidenebis (4,6-di-tert-butylphenol) with MgnBu_2: Efficient catalysts for ring-opening polymerization of caprolactone and L-Lactide, Macromolecules, 2004,37, 5155-5162
[5] Zhen, H. S.; Chisholm, M. H.; Gallucci, J. C, Three-coordinate zinc amide and phenoxide complexes supported by a bulky Schiff base ligand, Inorg. Chem., 2001,40,5051-5054
[6] Hitchcock, P. B.; Hill, M. S., Synthesis of C_2 and C_8 symmetric zinc complexes supported by bis(phosphinimino)methyl ligands and their use in ring-opening polymerization catalysis, J. Chem. Soc, Dalton Trans., 2002,4694-4702
[7] Tolman, W. B.; Williams, C. K.; Brooks, N. R., Metalloenzyme inspired dizinc catalyst for the polymerization of lactide, Chem. Commun., 2002,2132-2133.
[8] Ejfler, J.; Szafert, S.; Mierzwicki, K.; et al, Homo- and heteroleptic zinc aminophenolates as initiators for lactide polymerization, J. Chem. Soc, Dalton Trans., 2008, 6556-6562
[9] Richard, J. L.; Vernon, C. G.; Andrew, J. P. W.; et al, Combining Hard and Soft Donors in Early-Transition-Metal Olefin Polymerization Catalysts, Inorg. Chem., 2006, 45,511-513
[10] Han, X. H.; Yamamoto, Y.; Sugawara, K., Novel single or double insertion of alkynes into rhodium- and iridium-oxygen or -phosphorus atom bonds and transannular addition of 1-alkynes between the rhodium atom and the ipso-carbon atom of the phosphorus ligand, J. Chem. Soc, Dalton Trans., 2002, 195-211
[11] Herrmann, W. A.; Haider, J. J.; Fridgen, J.; et al, Chiral molybdenum(VI) and tungsten(VI) 2'-pyridinyl alcoholate complexes. Synthesis, structure and catalytic properties in asymmetric olefin epoxidation, J. Organomet. Chem., 2000, 603, 69-79
[12]Williams,C.K.;Breyfogle,L.E.;Young,V.G.;et al,A Highly Active Zinc Catalyst for the Controlled Polymerization of Lactide.J.Am.Chem.Soc.,2003,125,11350-11359
[13]Lucien Saussine;Fredy Speiser;Pieere Braunstein,Dinuclear nickel complexes with bidentate N,O ligands:synthesis,structure,and catalytic oligomerization of ethylene,Inorg.Chem.,2004,43,4234-4240
[14](a)Younkin,T.R.;Connor,E.F.;Henderson,J.I.;et al,Science 2000,288,1750-1751.
(b) Younkin,T.R.;Connor,E.F.;Henderson,J.I.;et al,Science,2000,287,460-462.
(c) Wang,C.;Friedrich,S.;Younkin,T.R.;et al,Organometallics,1998,17,3149-3151
[15](a) Brookhart,M.;Hicks,F.A.;Jenkins,J.C.,Organometallics,2003,22,3533-3545.
(b) Jenkins,J.C.;Brookhart,M.Organometallics,2003,22,250-256
[16](a) Zhao,W.;Qian,Y.,J.Inorg.Chem.Commun.,2004,7,459-461.
[17](a) Brookhart;Hicks,F.A.;Jenkins,J.C.,M.Organometallics,2003,22,3533-3545.;
(b)Jenkins,J.C.;Brookhart,M.Organometallics,2003,22,250-256
[18]Sun,W.H.;Zhang,W.;Gao,T.;et al,J.Organomet.Chem.,2004,43,869-873
[19]Lee,W.S.;Leung,H.K.;Cheng,L.S.;et al,Inorganica Chimica Acta,2004,357,4389-4395
[20]Herrmann,W.A.;Haider,J.J.;Fridgen,J.;et al,J.Organomet.Chem.,2000,603,69-79
[21]Yolanda Perez;Sonia Morante-Zarcero;Isabel Sierra;et al,Inorganica Chimica Acta,2007,360,607-618
[22]Fredy Speiser,Pieere Braunstein,Lucien Saussine,Dinuclear nickel complexes with bidentate N,O ligands:synthesis,structure,and catalytic oligomerization of ethylene,Inorg.Chem.,2004,43,4234-4240
[23]Harbi,T.A.M.;Joachim,S.;Peter,L.;et al,Synthesis and molecular structures of (2-dialkylaminophenyl)alcohols and of 2-phenylaminoalkyl-dimethylaminobenzene derivatives,Tetrahedron,2004,60,333-339
[24]Jolanta,E.;Michal,K.;Lucjan B.J.;et al,Highly efficient magnesium initiators for lactide polymerization,DaltonTrans,2005,2047-2050
[25] Wu, J. C; Hung, W. C.;Chen, Y. Z.; et al, Preparation, Characterization, and Catalytic Studies of Magnesium Phenoxides: Highly Active Initiators for Ring-Opening Polymerization of 1-Lactide, Organometallics, 2008, 27(19),4970-4978
[26] Gerhard, W. K.; Hendrikus, L.; Marius S.; et al, N-Lithiomethyl-N,N'N",N"-tetra-methyldiethylenetriamine: The First Alkyllithium Compound which is Monomeric in Hydrocarbons, Angew. Chem., 1992,104, 624
[27] Carsten S.; Viktoria, H. G., From the Alkyllithium Aggregate [{(n- BuLi)_2·PMDTA}_2] to Lithiated PMDTA, Angew. Chem., 2007, 46,4566-4569
[1](a)Albertson,A.C.;Varma,I.K.,Biomacromolecules,2003,4,1466;
(b)Kikkawa,Y.;Abe,H.;Ivata,T.;et al,Biomacromolecules,2002,3,350;
(c) Piddubnyak,V.;Kurcok,P.;Matuszowicz,A.;et al,Biomaterials,2004,25,5271;
(d) Yeh,J.;Ling,Y.;Karp,J.M.;et al,Biomaterials,2006,27,5391;
(e) Cheng,J.;Teply,B.A.;Sherifi,I.;et al,Biomaterials,2007,28,869
[2]James,L,Large-scale Production,properties and Commercial Applications of Polylactic Acid Polymer.Polymer Degradation and Stability,1998,59,145-152
[3]Gao,Z.T.;Lou,L.;Yin,J.B.,The Preparation and Properties of L-Lactide and Poly (L-Lactide),Polymermater LALS Science And Engineering,2003,19(2),72-75
[4]李曹,王远亮.聚乳酸制备研究进展,国外医学:生物医与艺工程分册,2002,25(6),274-278
[5]李瑞.21世纪绿色功能材料-聚乳酸,福建师范大学福清分校学报,2005,2,53-55
[6]朱久进,王远亮.丙交酯的合成与聚合,化工新型材料,2005,33,19-21
[7]高俊,江志荣.丙交酯开环法合成聚乳酸工艺探讨,合成技术及应用,2005,20,6-磊
[8](a)Gross,R.A.;Deng,F.,Enzyme-catalyzed Lactone Ring-opening Polymerizetions:Regioselectivity and the Preparation of a Star-shaped Polymer,ACS ,Symposium Series,2001,786,195-221;
(b) Chisholm,M.H.;Eilerts,N.W.;Huffman,et al,J.Am.Chem.Soc.2000,122,11845
[9]Dong,C.M.;Qiu,K.Y.;Gu Z.W.,Synthesis of Star-shaped Poly(D,L-lactic Acid-alt-Glycolic Acid)-b-Poly(L-Lactic acid) with the Poly(L-Lactic Acid-alt-Glycollc Acid) Macminitiator and Stannous Octoate Catalyst,Journal of Polymer Science,Part A:Polymer Chemistry,2002,40(3),409-415
[10]Jan,W.;Leenslag;Alert,J.,Resorbable Materials of Poly(L-laclide)Ⅶ in Vivo and in Vivo Degradation,Biomaterials,1987,8,311-314
[11]Kricheldorf,H.R.,Syntheses and application of polylactides,Chemophere,2001,43,49-54
[12]Degee,P.;Dubois,P.;Jer(o|¨)d.;Jacobsen,S.;Fritz,H.G.,Macromol.Symp.1999,144,289
[13](a) Darensbourg,D.J.;Holtcamp M.W.;Struck,G.E.;et al J.Am.Chem.Soc.1999,121,107.
(b) Darensbourg,D.J.;Wildeson,J.R.;Yarbrough,J.C.;et al,J.Am. Chem. Soc. 2000, 122, 12487. (c) Darensbourg, D. J.; Rainey, P.;Yarbrough, J.Inorg. Chem. 2001, 40, 986-993
[14] (a) Coates, G. W.; Cheng, M.; Lobkovsky, E. B., J. Am. Chem. Soc. 1998,120, 11018.
(b) Cheng, M; Attygalle, A. B.; Lobkovsky, E. B.; et al, J. Am. Chem. Soc. 1999,121,11583
[15] Chisholm, M. H.; Eilerts, N. W.; Huffman, J. C; et al, J. Am. Chem. Soc. 2000, 122,11845
[16] Chamberlain, B. M.; Cheng, M.; Moore, et al, J. Am. Chem. Soc. 2001, 123, 3229
[17] Chisholm, M. H.; Gallucci, J.; Phomphrai, K. Inorg. Chem., 2002, 41, 2785
[18] Dittrich W., The configuration of cellulose dissolved in iron-Sodiumtartrate,Macromol Chem, 1971,150,117
[19] (a)Kowalski, A.; Libiszowski, J.; Duda, A.; et al, Macromolecules, 2000, 33, 1964;
(b)Du, H.; Pang, X.; Yu, H.; et al, Macromolecules, 2007, 40, 1904;
(c) Chmura, A. J.;Davidson, M.G.; Jones, M. D.; et al, Macromolecules, 2006, 39, 7250
[20] (a)Bourissou, D.; Martin-Vaca, B.; Dumitrescu, A.; et al; Macromolecules, 2005, 38,9993;
(b) Sanda, F.; Sanada, H.; Shibasaki, Y.; et al, Macromolecules, 2002, 55, 680
[2]Jr.John Boor著,孙伯庆,张玉岜,栾瑛洁等译.齐格勒-纳塔催化剂和聚合[M].北京:化学工业出版社,1986.
[3]黄葆同,沈之荃等.烯烃双烯烃配位聚合进展[M].北京:科学出版社,1998.
[4]J.A.Ewen,Mechanisms of Stereochemical Control in Propylene Polymerizations with Soluble Group 4B Metallocene / Methylalumoxane Catalysts,J.Am.Chem.Soc.,1984,106,6355-6364.
[5]L.K.Johnson;M.F.Brookhart;C.M.Killian,New Pd(Ⅱ)-and Ni(Ⅱ)-Based Catalysts for Polynerization of Ethylene and α-Olefins,J.Am.Chem Soc.,1995,117,6414-6415.
[6]C.M.Killian;L.K.Johnson,et al.α-Olefins and Olefin Polymers and Processes Therefore[P].WO 9623010.1996-08-01.
[11]Caro,C.F.;Lappert,P.G.;Coordin.,M.F.;Merle,Review of Metal 1-azaallyl Complexes,Chem.Rev.,2001,219,605-663.
[12]Chakravarty,A.R.;Shamshoum,E.S.and Cotton,F.A.,2-Anilinopyridine complexes of dimolybdenum(Ⅱ) and ditungsten(Ⅱ),Inorg.Chem.,1984,23,4216-4221.
[13]Barr,D.;Mulvey,R.E.;Clegg,W.and Snaaith,R.,The structural isomers of {[ph(2-pyridyl)NLi].[O=P(NMe_2)_3]}_2:dimeric species with alternative central(LiN)_2and(LiO)_2 rings,the latter involving unprecedented neutral bridging oxygen ligands,J.Chem.Soc.,Chem.,Commun.,1984,700-703.
[14]Leskel(a|¨),M.and Polamo,M.,Syntheses and crystal structures of phenyl(2-pyridyl)-amido complexes of zirconium(Ⅳ),tantalum(Ⅴ) and niobium(Ⅴ),J.Chem.Soc.,Dalton Trans.,1996,4345-4246.
[15]Cotton,F.A.;Clerac,R.;Dunbar,K.R.;Pascual,I.;Murillo,C.A.and Wang,X.,Further Study of the Linear Trinickel(Ⅱ) Complex of Dipyridylamide,Inorg.Chem.,1999,38,2655-2657.
[16]Spannenberg,A.;Kempe,R.and Arndt,P.,Yttrate-Mediated Ligand Transfer and Direct Synthesis as a Route to Amidopalladium Complexes,Angew Chem.lnt.Ed.,1998,37,832-835.
[17]Edema.J.J.H.;Gambarotta,S.;Meetsma,A.;Veldman,N.and Spek,S.L.,Synthesis and structural features of novel vanadium(Ⅱ) amides,Inorg.Chem.,1991,30,2062-2066.
[18]Kempe,R.,Highlights der Renaissance der Amidometallchemie,Angew.Chem.,2000, 112, 478-504.
[19] Sekutowski, J. C.; Niswander, R. H.; Cotton, F. A., Homologous chromium, molybdenum, and tungsten compounds with very short quadruple bonds, Inorg.Chem., 1978,77,3541-3545.
[20] Lu, J. Y.; Wang, R. J.; Cabrera, B. R., Chemical Rearrangement under Hydrothermal Conditions: Formation of Polymeric Chains (CuX)2(dpiz) and (CuX)3(dpiz) (X =Cl, Br; dpiz=Dipyridot[1,2-a:2',3'-d]imidazole), Inorg. Chem., 1998, 37, 4480-4481.
[21] Clerac, R.; Cotton, F. A.; Dunbar, K. R.; et al, A New Linear Tricobalt Compound with Di(2-pyridyl)amide (dpa) Ligands: Two-Step Spin Crossover of [Co3(dpa)4C12][BF4],J. Am. Chem. Soc, 2000,122,2272-2278.
[22] Lee, C. F.; Chin, K. F.; Peng, S. M.; et al, A luminescent tetrameric zinc(II) complex containing the 7-azaindolate ligand. Photophysical properties and crystal structure, J.Chem. Soc, Dalton Trans., 1993,467-469.
[23] James, B.; Melvyn, K., The coordination chemistry of the amidine ligand, Coord.Chem. Rev., 1994,133,219
[24] Laurence, B. M., Lappert, M. F. and Severn, J. R., The Chemistry of (?)-Diketiminato-metal Complexes, Chem. Rev. 2002, 702, 3031-3065
[25] Ejfler, J.; Szafert, S.; Mierzwicki, K.; et al, Homo- and heteroleptic zinc aminophenolates as initiators for lactide polymerization, J. Chem. Soc, Dalton Trans., 2008, 6556-6562.
[26] Chen, H. Y.; Lin C. C; Tang, H. Y., Ring-Opening Polymerization of Lactides Initiated by Zinc Alkoxides Derived from NNO-Tridentate Ligands,Macromolecules, 2006, 39, 3745-3752
[27] Jolanta, E.; Michai, K.; Lucjan B.; et al, Highly efficient magnesium initiators for lactide polymerization, DaltonTrans, 2005, 2047-2050
[28] Fredy Speiser; Lucien Saussine; Pieere Braunstein, Dinuclear nickel complexes with bidentate N,0 ligands: synthesis, structure, and catalytic oligomerization of ethylene,Inorg. Chem., 2004, 43, 4234-4240.
[29] (a)Younkin, T. R.; Connor, E. F.; Henderson, J. I.; et al, Science 2000, 288,1750-1751.
(b)Wang, C.; Friedrich, S.; Younkin, T. R.; et al, Organometallics, 1998,17,3149-3151
[30](a)Hicks,F.A.;Brookhart,M.;Jenkins,J.C.,Organometallics,2003,22,3533-3545.
(b) Jenkins,J.C.;Brookhart,M.Organometallics,2003,22,250-256.
[31](a)Qian,Y.;Zhao,W.,J.Inorg.Chem.Commun.,2004,7,459-461.
(b) Sun,W.H.;Zhang,W.;Gao,T.;et al,J.Organomet.Chem.,2004,43,869-873.
[32]Lee,W.S.;Leung,H.K.;Cheng,L.S.;et al,Inorganica Chimica Acta,2004,357,4389-4395
[33]Herrmann,W.A.;Haider,J.J.;Fridgen,J.;et al,d.Organomet.Chem.,2000,603,69-79
[34]Yolanda Perez;Sonia Morante-Zarcero;Isabel Sierra;et al,Inorganica Chimica Acta,2007,360,607-618
[35]Usui,H.;Watanable,Y.;Kanqo,M.J.,Heterocycl.Chem.,1993,30(2),551
[36]Dagorne,S.;Guzei,I.A.;Coles,M.P.;et al,J.Am.Chem.Soc.,2000,122,274;
[37]Dagorne,S.;Jordan,R.F.;Young,V.G.,Organometallics,1999,18,4619
[38]Coles,M.P.;Swenson,D.C.;Jordan,R.F.;et al,Organometallics,1998,17,4042
[39]Coles,M.P.;Swenson,D.C.;Jordan,R.F.;et al,Organometallics,1997,16,5183
[40]Talarico,G.;Budzelaar,P.H.M.;Organometallics,2000,19,5691
[41]Rillich,M;Komber,H.;Boechme,F.;Poiym.Bull(Berlin),1993,31(4),381[42]徐振元,刘毅锋,严巍等.浙江化工,1988,19(6),1
[43]Van,V.P.I.;Van,K.G.;Vcieze,K.J.,Organomet.Chem.,1979,179(1),89
[44]Sanzhiafiapor,D.B.;Tsyganov,A.D.;Doroshenko,Y.E.;et al.,SU 1,736,978
[45]Knyaztva,V.F.;Granik,V.G.;Khim,F.Zh.,1981,15(5),44
[46]Gupten,J.T.;Idoux,J.P.;Leonard,R.;et al.,Synth.Common.,1983,13(13),1083
[47]Basink,V.A.,Oaigins Life Evol.Biosphere,1992,22(6),333
[48]Xia,A.i.;Hani,M.E.;Mary J.H.;et al,Synthesis,structure,and properties of magnesium complexes containing cyclopentadienyl and amidinate ligand sets,J.Organomet.Chem.,2003,682,224-232
[49]李瑞.21世纪绿色功能材料-聚乳酸,福建师范大学福清分校学报,2005,2,53-55
[50]朱久进,王远亮.丙交酯的合成与聚合,化工新型材料,2005,33,19-21.
[51]高俊,江志荣.丙交酯开环法合成聚乳酸工艺探讨,合成技术及应用,2005,20,6-8
[52]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
[53]Das,K.G.,Controlled release technology bioengineering aspects.New York:JohnWiley and Sons,1983
[54]俞耀庭,张兴栋.生物医用材料,天津:天津大学出版社,2000.181
[55]牛旭锋,罗彦凤,王远亮,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
[56](a)Chisholm,M.H.;Gallucci,J.,Lactide polymerization by well-difined calcium coordination complexes:comparisons with related magnesium and zinc chemistry,Chem.Commum.,2003,48-49
[57]Chamberlain,B.M.;Cheng,M.;Moore,D.R.;et al,Polymerization of Lactide with zinc and magnesium β-diiminate complexes:stereocontrol and mechanism,J.Am.Chem.Soc.,2001,123,3229-3231
[58]Shueh,M.L.;Lin,C.C.;Wang,Y.S.,Reactions of 2,2'-Methyl-enebis (4-chloro-6-isopropyl-3-methylphenol) and 2,2'-Ethylidenebis(4,6-di-tertbutylphenol)with MgnBu_2:Efficient catalysts for ring-opening polymerization of caprolactone and L-Lactide,Macromolecules,2004,37,5155-5162
[59]Chisholm,M.H.;Zhen,H.S.;Gallucci,J.C.,Three-coordinate zinc amide and phenoxide complexes supported by a bulky Schiff base ligand,Inorg.Chem.,2001,40,5051-5054
[60]Hitchcock,P.B.;Hill,M.S.,Synthesis of C_2 and C_8 symmetric zinc complexes supported by bis(phosphinimino)methyl ligands and their use in ring-opening polymerization catalysis,J.Chem.Soc.,Dalton Trans.,2002,4694-4702
[61]Williams,C.K.;Tolman,W.B.;Brooks,N.R.,Metalloenzyme inspired dizinc catalyst for the polymerization of lactide,Chem.Commun.,2002,2132-2133.
[62]Yu,T.L.;Wu,J.C.,Recent developments in main group metal complexes catalyzed/initiated polymerization of lactides and related cyclic esters.Coordination Chemistry Reviews.2006,250,602-626
[63]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
[64]崔冬梅,朱宁,程建华,陈文启,唐涛,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.
[65]刘小兰,赵茹,刘晓红,岳俊杰,缪方明,陈克.新型桥连双锌配合物的合成和结构,化学学报,2003,61,578-583
[66]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
[67]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
[68]Dubois,P.;Jacobs,C.;Jerome,R.;et al,Macromolecular engineering of polylactones and polylactides.Mechanism and kinetics of lactide homopolymerization by aluminum isopropoxide,Macromolecules,1991,24,2266-2270
[69]甘志华,张杰,胡平,周新林.丙交酯的制备及其开环聚合,吉林工业大学学报1998,28,266-270
[70]Ford,T.M.;Drysdale N.E.,ACS Polymer Prep,1992,33,463-475
[71]王小莺,廖凯荣,伍青,全大萍.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(自然科学皈),2005,44,42-45
[72]廖凯荣,王小莺,伍青,全大萍,乙酰丙酮铁催化丙交酯开环聚合的研究,高分子学报,2005,1,113-118
[73]Janeczek,H.;Ddbrzynski,P.;Kasperczyk,J.;et al.Synthesis of biodegradable glycolidegradable glycolide/L-Lactide copolymers using iron compounds as initiators,Polymer,2002,43:2595-2600
[74]Hillmyer,M.A.;Monnier,S.M.;O'Keefe,B.J.;et al.Rapid and controlled polymerization of lactide by structurally characterized ferric alkoxide,J Am Chem Soc,2001,123:339-340
[75]Wardla,W.W.;Multani,R.K.;Bradley,D.C.,Structural chemidtry of the alkoxides (X).Primary alkoxides of tervalent iron,J Chem Soc,1958,126-129
[1]Ziegler,K.,Breil,H.,Martion,H.,DBP973626,1953,11,17.
[2]Natta,G.,Pino,P.,Mazzati,G.,US.Patent 3715344,Ital Priority,1954,6,8.
[3]Sinn,H.;Woldt,R.;Kaminsky,W.;Vollmer,H.J.,"Living Polymers" on Polymerization with Extremely Productive Ziegler Catalysts.,Angew.Chem.,Int.Ed.,1980,19,390-392.
[4]Johnson,L.K.;Brookhart,M.;Killian,C.M.,New Pd(Ⅱ) and Ni(Ⅱ) Based Catalysts for Polymerization of Ethylene and.alpha.-Olefins,J.Am.Chem.Soc.,1995,117,6414-6415.
[5]Bennett,A.M.A.;Small,B.L.;Brookhart,M.,Highly Active Iron and Cobalt Catalysts for the Polymerization of Ethylene,J.Am.Chem.Soc.,1998,120,4049-4051.
[6]Britovsek,G.J.P.;Gibson,V.C.;Kimberley,B.S.;et al,Novel olefin polymerization catalysts based on iron and cobalt,Chem.Commun.,1998,7,849-851.
[7]Coles,M.P.,Application of neutral amidines and guanidines in coordination chemistry,Dalton Trans.,2006,985-1001
[8]James,B.;Melvyn,K.,The coordination chemistry of the amidine ligand,Coord.Chem.Rev.,1994,133,219
[9]Pace,S.;Bailey,P.J.,The coordination chemistry of guanidines and guanidinates,Coord.Chem.Rev.,2001,214,91
[10]K(o|¨)hn,U.;G(u|¨)nther,W.;G(o|¨)rls,H.;et al,Preparation of chiral thioureas,ureas and guanidines from(S)-2-(N,N-dialkylaminomethyl)pyrrolidines,Tetrahedron:Asymmetry,2004,15,1419-1426
[11]Xia,A.B.;Hani M.El-K.;Mary J.H.;et al,Synthesis,structure,and properties of magnesium complexes containing cyclopentadienyl and amidinate ligand sets,J.Organomet.Chem.,2003,682,224-232
[12] (a) S. Dagorne; I.A. Guzei; M.P. Coles; et al,J. Am.Chem. Soc, 2000,122, 274;
(b) S.Dagorne; V.G. Young; R.F. Jordan, Organometallics, 1999, 18, 4619;
(c) D.C.Swenson; M.P. Coles; V.G. Young; R.F. Jordan, Organometallics, 1998, 17, 4042;
(d) M.P. Coles; D.C. Swenson; R.F. Jordan; et al, Organometallics, 1997,16, 5183;
(e) P.H.M. Budzelaar; G. Talarico, Organometallics, 2000,19, 5691.
[13] (a) V. Volkis; E. Nelkenbaum; A. Lisovskii; et al, J. Am. Chem. Soc., 2003, 125,2179;
(b) S.K. Spitzmesser; V.C. Gibson, Chem. Rev., 2003, 103, 283;
(c) R.J.Keaton; L.A. Koterwas; J.C. Fettinger; et al, J. Am. Chem. Soc., 2002,124, 5932;
(d)T.Y. Meyer; J.M. Decker; S.J. Geib, Organometallics, 1999,18, 4417.
[14] J. Barker; N.C. Blacker; P.R. Phillips; et al, J. Chem. Soc. Dalton Trans. 1996,431.
[15] Mansfield, N. E.; Grundy J.; Coles M. P.; et al, A Conformational Study of Phospha(III)- and Phospha(V)-guanidine Compounds, J. Am. Chem. Soc., 2006, 128,13879-13893
[16] Cole, M. L.; Junk, P. C.;Louis, L. M., Synthesis and structural characterisation of some novel lithium and sodium N,N_-di(para-tolyl)formamidinate complexes, J.Chem. Soc, Dalton Trans., 2002, 3906-3914
[17] Dagorne, S.; Guzei, I. A.; Coles, M. P.; et al, Synthesis and Structures of Cationic Aluminum and Gallium Amidinate Complexes, J. Am. Chem. Soc. 2000, 122,274-289
[18] Andrews, P. C; Brym M.; Jones, C.; et al, Inorganica Chimica Acta, 2006, 359,355-363
[19] Mansfield, N. E.; Coles, M. P.; Avent, A. G.; et al, Coordination Chemistry of Isomeric Mixtures of Linked Di(phosphaguanidine) Compounds: A Spectroscopic and Crystallographic Study, Organometallics, 2006,25, 2470-2474
[1]Wu,J.C.;Yu,T.L.;Chen,C.T.;et al,Recent developments in main group metal complexes catalyzed/initiated polymerization of lactides and related cyclic esters,Coordin.Chem.Rev.,2006,250,602-626
[2](a) Gallucci,J.;Chisholm,M.H.,Lactide polymerization by well-difined calcium coordination complexes:comparisons with related magnesium and zinc chemistry,Chem.Commum.,2003,48-49
(b)Chisholm,M.H.;Eilerts,N.W.;Huffman,J.C.;et al,Molecular design of single-site metal alkoxide catalyst precursors for ring-opening polymerization reactions leading to polyoxygenates.1.Polylactide formation by achiral and chiral magnesium and zinc alkoxides,(η~3-L)MOR,where L=Trispyrazolyl-and Trisindazolylborate ligands,J.Am.Chem.Soc.,2000,122,11845-11854
[3] (a)Chamberlain, B. M.; Cheng, M.; Moore, D. R.; et al, Polymerization of Lactide with zinc and magnesium P-diiminate complexes: stereocontrol and mechanism, J. Am.Chem. Soc., 2001,123, 3229-3231
(b)Hormnirun,P.; Marshall, E. L.; Gibson,V. C.; et al, Remarkable Stereoconteol in Polymerization of Racemic Lactide Using Aluminum Initiators Supported by Tetradentate Aminophenoxide Ligands, J. Am. Chem. Soc, 2004,126,2688-2689
[4] Lin, C. C; Shueh, M. L.; Wang, Y. S., Reactions of 2,2'-Methylenebis (4-chloro-6-isopropyl-3-methylphenol) and 2,2'-Ethylidenebis (4,6-di-tert-butylphenol) with MgnBu_2: Efficient catalysts for ring-opening polymerization of caprolactone and L-Lactide, Macromolecules, 2004,37, 5155-5162
[5] Zhen, H. S.; Chisholm, M. H.; Gallucci, J. C, Three-coordinate zinc amide and phenoxide complexes supported by a bulky Schiff base ligand, Inorg. Chem., 2001,40,5051-5054
[6] Hitchcock, P. B.; Hill, M. S., Synthesis of C_2 and C_8 symmetric zinc complexes supported by bis(phosphinimino)methyl ligands and their use in ring-opening polymerization catalysis, J. Chem. Soc, Dalton Trans., 2002,4694-4702
[7] Tolman, W. B.; Williams, C. K.; Brooks, N. R., Metalloenzyme inspired dizinc catalyst for the polymerization of lactide, Chem. Commun., 2002,2132-2133.
[8] Ejfler, J.; Szafert, S.; Mierzwicki, K.; et al, Homo- and heteroleptic zinc aminophenolates as initiators for lactide polymerization, J. Chem. Soc, Dalton Trans., 2008, 6556-6562
[9] Richard, J. L.; Vernon, C. G.; Andrew, J. P. W.; et al, Combining Hard and Soft Donors in Early-Transition-Metal Olefin Polymerization Catalysts, Inorg. Chem., 2006, 45,511-513
[10] Han, X. H.; Yamamoto, Y.; Sugawara, K., Novel single or double insertion of alkynes into rhodium- and iridium-oxygen or -phosphorus atom bonds and transannular addition of 1-alkynes between the rhodium atom and the ipso-carbon atom of the phosphorus ligand, J. Chem. Soc, Dalton Trans., 2002, 195-211
[11] Herrmann, W. A.; Haider, J. J.; Fridgen, J.; et al, Chiral molybdenum(VI) and tungsten(VI) 2'-pyridinyl alcoholate complexes. Synthesis, structure and catalytic properties in asymmetric olefin epoxidation, J. Organomet. Chem., 2000, 603, 69-79
[12]Williams,C.K.;Breyfogle,L.E.;Young,V.G.;et al,A Highly Active Zinc Catalyst for the Controlled Polymerization of Lactide.J.Am.Chem.Soc.,2003,125,11350-11359
[13]Lucien Saussine;Fredy Speiser;Pieere Braunstein,Dinuclear nickel complexes with bidentate N,O ligands:synthesis,structure,and catalytic oligomerization of ethylene,Inorg.Chem.,2004,43,4234-4240
[14](a)Younkin,T.R.;Connor,E.F.;Henderson,J.I.;et al,Science 2000,288,1750-1751.
(b) Younkin,T.R.;Connor,E.F.;Henderson,J.I.;et al,Science,2000,287,460-462.
(c) Wang,C.;Friedrich,S.;Younkin,T.R.;et al,Organometallics,1998,17,3149-3151
[15](a) Brookhart,M.;Hicks,F.A.;Jenkins,J.C.,Organometallics,2003,22,3533-3545.
(b) Jenkins,J.C.;Brookhart,M.Organometallics,2003,22,250-256
[16](a) Zhao,W.;Qian,Y.,J.Inorg.Chem.Commun.,2004,7,459-461.
[17](a) Brookhart;Hicks,F.A.;Jenkins,J.C.,M.Organometallics,2003,22,3533-3545.;
(b)Jenkins,J.C.;Brookhart,M.Organometallics,2003,22,250-256
[18]Sun,W.H.;Zhang,W.;Gao,T.;et al,J.Organomet.Chem.,2004,43,869-873
[19]Lee,W.S.;Leung,H.K.;Cheng,L.S.;et al,Inorganica Chimica Acta,2004,357,4389-4395
[20]Herrmann,W.A.;Haider,J.J.;Fridgen,J.;et al,J.Organomet.Chem.,2000,603,69-79
[21]Yolanda Perez;Sonia Morante-Zarcero;Isabel Sierra;et al,Inorganica Chimica Acta,2007,360,607-618
[22]Fredy Speiser,Pieere Braunstein,Lucien Saussine,Dinuclear nickel complexes with bidentate N,O ligands:synthesis,structure,and catalytic oligomerization of ethylene,Inorg.Chem.,2004,43,4234-4240
[23]Harbi,T.A.M.;Joachim,S.;Peter,L.;et al,Synthesis and molecular structures of (2-dialkylaminophenyl)alcohols and of 2-phenylaminoalkyl-dimethylaminobenzene derivatives,Tetrahedron,2004,60,333-339
[24]Jolanta,E.;Michal,K.;Lucjan B.J.;et al,Highly efficient magnesium initiators for lactide polymerization,DaltonTrans,2005,2047-2050
[25] Wu, J. C; Hung, W. C.;Chen, Y. Z.; et al, Preparation, Characterization, and Catalytic Studies of Magnesium Phenoxides: Highly Active Initiators for Ring-Opening Polymerization of 1-Lactide, Organometallics, 2008, 27(19),4970-4978
[26] Gerhard, W. K.; Hendrikus, L.; Marius S.; et al, N-Lithiomethyl-N,N'N",N"-tetra-methyldiethylenetriamine: The First Alkyllithium Compound which is Monomeric in Hydrocarbons, Angew. Chem., 1992,104, 624
[27] Carsten S.; Viktoria, H. G., From the Alkyllithium Aggregate [{(n- BuLi)_2·PMDTA}_2] to Lithiated PMDTA, Angew. Chem., 2007, 46,4566-4569
[1](a)Albertson,A.C.;Varma,I.K.,Biomacromolecules,2003,4,1466;
(b)Kikkawa,Y.;Abe,H.;Ivata,T.;et al,Biomacromolecules,2002,3,350;
(c) Piddubnyak,V.;Kurcok,P.;Matuszowicz,A.;et al,Biomaterials,2004,25,5271;
(d) Yeh,J.;Ling,Y.;Karp,J.M.;et al,Biomaterials,2006,27,5391;
(e) Cheng,J.;Teply,B.A.;Sherifi,I.;et al,Biomaterials,2007,28,869
[2]James,L,Large-scale Production,properties and Commercial Applications of Polylactic Acid Polymer.Polymer Degradation and Stability,1998,59,145-152
[3]Gao,Z.T.;Lou,L.;Yin,J.B.,The Preparation and Properties of L-Lactide and Poly (L-Lactide),Polymermater LALS Science And Engineering,2003,19(2),72-75
[4]李曹,王远亮.聚乳酸制备研究进展,国外医学:生物医与艺工程分册,2002,25(6),274-278
[5]李瑞.21世纪绿色功能材料-聚乳酸,福建师范大学福清分校学报,2005,2,53-55
[6]朱久进,王远亮.丙交酯的合成与聚合,化工新型材料,2005,33,19-21
[7]高俊,江志荣.丙交酯开环法合成聚乳酸工艺探讨,合成技术及应用,2005,20,6-磊
[8](a)Gross,R.A.;Deng,F.,Enzyme-catalyzed Lactone Ring-opening Polymerizetions:Regioselectivity and the Preparation of a Star-shaped Polymer,ACS ,Symposium Series,2001,786,195-221;
(b) Chisholm,M.H.;Eilerts,N.W.;Huffman,et al,J.Am.Chem.Soc.2000,122,11845
[9]Dong,C.M.;Qiu,K.Y.;Gu Z.W.,Synthesis of Star-shaped Poly(D,L-lactic Acid-alt-Glycolic Acid)-b-Poly(L-Lactic acid) with the Poly(L-Lactic Acid-alt-Glycollc Acid) Macminitiator and Stannous Octoate Catalyst,Journal of Polymer Science,Part A:Polymer Chemistry,2002,40(3),409-415
[10]Jan,W.;Leenslag;Alert,J.,Resorbable Materials of Poly(L-laclide)Ⅶ in Vivo and in Vivo Degradation,Biomaterials,1987,8,311-314
[11]Kricheldorf,H.R.,Syntheses and application of polylactides,Chemophere,2001,43,49-54
[12]Degee,P.;Dubois,P.;Jer(o|¨)d.;Jacobsen,S.;Fritz,H.G.,Macromol.Symp.1999,144,289
[13](a) Darensbourg,D.J.;Holtcamp M.W.;Struck,G.E.;et al J.Am.Chem.Soc.1999,121,107.
(b) Darensbourg,D.J.;Wildeson,J.R.;Yarbrough,J.C.;et al,J.Am. Chem. Soc. 2000, 122, 12487. (c) Darensbourg, D. J.; Rainey, P.;Yarbrough, J.Inorg. Chem. 2001, 40, 986-993
[14] (a) Coates, G. W.; Cheng, M.; Lobkovsky, E. B., J. Am. Chem. Soc. 1998,120, 11018.
(b) Cheng, M; Attygalle, A. B.; Lobkovsky, E. B.; et al, J. Am. Chem. Soc. 1999,121,11583
[15] Chisholm, M. H.; Eilerts, N. W.; Huffman, J. C; et al, J. Am. Chem. Soc. 2000, 122,11845
[16] Chamberlain, B. M.; Cheng, M.; Moore, et al, J. Am. Chem. Soc. 2001, 123, 3229
[17] Chisholm, M. H.; Gallucci, J.; Phomphrai, K. Inorg. Chem., 2002, 41, 2785
[18] Dittrich W., The configuration of cellulose dissolved in iron-Sodiumtartrate,Macromol Chem, 1971,150,117
[19] (a)Kowalski, A.; Libiszowski, J.; Duda, A.; et al, Macromolecules, 2000, 33, 1964;
(b)Du, H.; Pang, X.; Yu, H.; et al, Macromolecules, 2007, 40, 1904;
(c) Chmura, A. J.;Davidson, M.G.; Jones, M. D.; et al, Macromolecules, 2006, 39, 7250
[20] (a)Bourissou, D.; Martin-Vaca, B.; Dumitrescu, A.; et al; Macromolecules, 2005, 38,9993;
(b) Sanda, F.; Sanada, H.; Shibasaki, Y.; et al, Macromolecules, 2002, 55, 680