Bimetallic anilido-aldimine Al or Zn complexes for efficient ring-opening polymerization of epsilon-caprolactone.

Four bimetallic Al or Zn complexes supported by anilido-aldimine ligands (o-C6H4(NHAr)-CH=N)2CH2CH2 (Ar = 2,6-Me2C6H3,L1H2; Ar = 2,6-iPr2C6H3, L2H2) have been synthesized and characterized. Treatment of L1H2 or L2H2 with two equiv. of AlMe3 gives bimetallic complex L1(AlMe2)2 1 or L2 (AlMe2)2 2, respectively. Reaction of L1H2 or L2H2 with two equiv. of ZnEt2 leads to bimetallic complex L1(ZnEt)2 3 or L2(ZnEt)2 4, respectively. All of the complexes 1-4 are efficient catalysts for ring-opening polymerization of epsilon-caprolactone (CL) in the presence of benzyl alcohol and catalyze the polymerization of CL in living fashion yielding polymers with a narrow polydispersity index. The activity of bimetallic Zn complexes 3 and 4 is higher than bimetallic Al complexes 1 and 2.

[1]  Ewan E. Delbridge,et al.  Synthesis and characterisation of lanthanide phenolate compounds and their catalytic activity towards ring-opening polymerisation of cyclic esters. , 2007, Dalton transactions.

[2]  Kuldip Singh,et al.  Sterically variable dizinc complexes bearing bis(iminopyridyl)phenolate ligands: synthesis, structures and reactivity studies. , 2007, Dalton transactions.

[3]  Yingming Yao,et al.  Controlled syntheses, characterization, and reactivity of neutral and anionic lanthanide amides supported by methylene-linked bis(phenolate) ligands. , 2007, Inorganic chemistry.

[4]  Yingming Yao,et al.  Novel mixed-metal alkoxide clusters of lanthanide and sodium: synthesis and extremely active catalysts for the polymerization of epsilon-caprolactone and trimethylene carbonate. , 2007, Inorganic chemistry.

[5]  I. Císařová,et al.  Aluminum(III) complexes containing O,O chelating ligand , 2007 .

[6]  M. Hillmyer,et al.  Structural and mechanistic studies of bis(phenolato)amine zinc(II) catalysts for the polymerization of ε-caprolactone , 2007 .

[7]  Gaosheng Yang,et al.  Synthesis, Structure, and Diverse Catalytic Activities of [Ethylenebis(indenyl)]lanthanide(III) Amides on N−H and C−H Addition to Carbodiimides and ε-Caprolactone Polymerization , 2007 .

[8]  Shaoyin Wang,et al.  Synthesis, characterization, and catalytic activity of divalent organolanthanide complexes with new tetrahydro-2H-pyranyl-functionlized indenyl ligands , 2007 .

[9]  S. Bellemin‐Laponnaz,et al.  Well‐Defined Cationic Alkyl– and Alkoxide–Aluminum Complexes and Their Reactivity with ε‐Caprolactone and Lactides , 2007 .

[10]  Shuangliu Zhou,et al.  Synthesis, Characterization, and Catalytic Activity of Some Neodymium(III), Ytterbium(II), and Europium(II) Complexes with Pyrrolidinyl‐ and Piperidinyl‐Functionalized Indenyl Ligands , 2007 .

[11]  Chun-yan Qi,et al.  Lithium, Magnesium, and Zinc Iminophosphorano(8-quinolyl)methanide Complexes: Syntheses, Characterization, and Activity in ε-Caprolactone Polymerization , 2007 .

[12]  A. Vega,et al.  Coordination and Reactivity Diversity of N-Piperidineethyl-Functionalized Indenyl Ligands: Synthesis, Structure, Theoretical Calculation, and Catalytic Activity of Organolanthanide Complexes with the Ligands , 2007 .

[13]  J. Feijen,et al.  Ring‐opening polymerization of substituted ε‐caprolactones with a chiral (salen) AlOiPr complex , 2007 .

[14]  Gene-Hsiang Lee,et al.  Four-and five-coordinate magnesium compounds containing ketiminate ligands. synthesis and characterization of L2Mg, L2Mg(LH), and L2Mg(Py), where L = MeC(O)CHC(NAr)Me , 2007 .

[15]  Huadong Guo,et al.  Ytterbium(II) complex bearing a diaminobis(phenolate) ligand: synthesis, structure, and one-electron-transfer and epsilon-caprolactone polymerization reactions. , 2007, Inorganic chemistry.

[16]  Ewan E. Delbridge,et al.  Synthesis, structure and oxidation of new ytterbium(II) bis(phenolate) compounds and their catalytic activity towards ε-caprolactone , 2007 .

[17]  A. White,et al.  Synthesis and structures of bimetallic and polymeric zinc coordination compounds supported by salicylaldiminato and anilido-aldimine ligands. , 2007, Dalton transactions.

[18]  M. Eisen,et al.  Titanium and Zirconium Complexes for Polymerization of Propylene and Cyclic Esters , 2007 .

[19]  S. M. Humphrey,et al.  Titanium, zinc and alkaline-earth metal complexes supported by bulky O,N,N,O-multidentate ligands: syntheses, characterisation and activity in cyclic ester polymerisation. , 2006, Dalton transactions.

[20]  A. F. Johnson,et al.  Group 4 Complexes with Aminebisphenolate Ligands and Their Application for the Ring Opening Polymerization of Cyclic Esters , 2006 .

[21]  Mao-Lin Hsueh,et al.  Well-defined sterically hindered zinc aryloxides: Excellent catalysts for ring-opening polymerization of ɛ-caprolactone and l-lactide , 2006 .

[22]  Zhong‐Xia Wang,et al.  Synthesis and characterization of aluminum(III) and tin(II) complexes supported by diiminophosphinate ligands and their application in ring‐opening polymerization catalysis of ε‐caprolactone , 2006 .

[23]  Yingming Yao,et al.  Homopolymerization of cyclic esters initiated by lanthanide isopropoxides supported by 2,2′‐ethylene‐bis(4,6‐di‐tert‐butylphenolate) ligands , 2006 .

[24]  Yong Zhang,et al.  Synthesis, structure of functionalized N-heterocyclic carbene complexes of Fe(II) and their catalytic activity for ring-opening polymerization of ε-caprolactone , 2006 .

[25]  H. Yun,et al.  Bimetallic fluorine-substituted anilido-aldimine zinc complexes for CO2/(cyclohexene oxide) copolymerization. , 2006, Inorganic chemistry.

[26]  Matthew D. Jones,et al.  Synthesis and X-ray structures of new titanium(IV) aryloxides and their exploitation for the ring opening polymerization of epsilon-caprolactone. , 2006, Inorganic chemistry.

[27]  Jincai Wu,et al.  Recent developments in main group metal complexes catalyzed/initiated polymerization of lactides and related cyclic esters , 2006 .

[28]  Matthew D. Jones,et al.  Group 4 complexes of amine bis(phenolate)s and their application for the ring opening polymerisation of cyclic esters. , 2006, Dalton transactions.

[29]  Charlotte K. Williams,et al.  Comparison of structurally analogous Zn2, Co2, and Mg2 catalysts for the polymerization of cyclic esters. , 2006, Dalton transactions.

[30]  K. Lyssenko,et al.  Interaction of titanium(III) zwitterionic complex Cp[η5-C5H4B(C6F5)3]Ti with organic halides: Synthesis and X-ray crystal structure determination of zwitterionic titanocene monohalides Cp[η5-C5H4B(C6F5)3]TiX (X = Cl, Br) and their catalytic activity in the ring-opening polymerization of ε-caprolacto , 2006 .

[31]  P. Cassagnau,et al.  Ring-Opening Polymerization of ε-Caprolactone Initiated with Titanium n-Propoxide or Titanium Phenoxide , 2006 .

[32]  L. Sánchez-Barba,et al.  Ligand transfer reactions of mixed-metal lanthanide/magnesium allyl complexes with β-diketimines: Synthesis, structures, and ring-opening polymerization catalysis , 2006 .

[33]  A. Tuzi,et al.  Neutral and Cationic Heteroscorpionate Aluminum Complexes: Synthesis, Structure, and Ring-Opening Polymerization of ε-Caprolactone , 2006 .

[34]  R. Welter,et al.  An Aluminum Complex Supported by a Fluorous Diamino-Dialkoxide Ligand for the Highly Productive Ring-Opening Polymerization of epsilon-Caprolactone , 2005 .

[35]  C. Qian,et al.  Homolysis of the Ln–N bond: Synthesis, characterization and catalytic activity of organolanthanide(II) complexes with furfuryl- and tetrahydrofurfuryl-functionalized indenyl ligands , 2005 .

[36]  H. Lee,et al.  Synthesis and characterization of lithium and yttrium complexes containing tridentate pyrrolyl ligands. Single-crystal X-ray structures of {Li[C4H2N(CH2NMe2)2-2,5]}2 (1) and {[C4H2N(CH2NMe2)2-2,5]YCl2(μ-Cl) · Li(OEt2)2}2 (2) and ring-opening polymerization of ε-caprolactone , 2005 .

[37]  J. Lewiński,et al.  Chelation Effect in Polymerization of Cyclic Esters by Metal Alkoxides: Structure Characterization of the Intermediate Formed by Primary Insertion of Lactide into the Al−OR Bond of an Organometallic Initiator , 2005 .

[38]  Jincai Wu,et al.  Catalysts for the ring-opening polymerization of ε-caprolactone and l-lactide and the mechanistic study , 2005 .

[39]  J. Okuda,et al.  Synthesis, Structural Characterization, and Catalytic Properties of Group 4 Metal Complexes Incorporating a Phosphorus-Bridged Indenyl-Carboranyl Constrained-Geometry Ligand , 2005 .

[40]  N. Nomura,et al.  Salicylaldimine-Aluminum Complexes for the Facile and Efficient Ring-Opening Polymerization of ∊-Caprolactone , 2005 .

[41]  Hsuan‐Ying Chen,et al.  A highly efficient initiator for the ring-opening polymerization of lactides and ∈-caprolactone : A kinetic study , 2005 .

[42]  Guanghua Li,et al.  Dialkylaluminum Complexes with Chelating Anilido-Imine Ligands: Synthesis, Structures, and Luminescent Properties , 2005 .

[43]  Hoseop Yun,et al.  Bimetallic anilido-aldimine zinc complexes for epoxide/CO2 copolymerization. , 2005, Journal of the American Chemical Society.

[44]  J. Lewiński,et al.  Towards the Nature of Active Sites in Polymerization of Cyclic Esters Initiated by Aluminium Alkoxides: First Structurally Authenticated Aluminium- e-Caprolactone Complex , 2004 .

[45]  Bor-Hunn Huang,et al.  Aluminum complexes supported by tridentate aminophenoxide ligand as efficient catalysts for ring-opening polymerization of epsilon-caprolactone , 2004 .

[46]  M. Dranka,et al.  Simple generation of cationic aluminum alkyls and alkoxides based on the pendant arm tridentate schiff base. , 2004, Inorganic chemistry.

[47]  R. Jerome,et al.  Recent developments in the ring-opening polymerization of epsilon-caprolactone and derivatives initiated by tin(IV) alkoxides , 2004 .

[48]  Bor-Hunn Huang,et al.  Reactions of 2,2‘-Methylenebis(4-chloro-6-isopropyl-3-methylphenol) and 2,2‘-Ethylidenebis(4,6-di-tert-butylphenol) with MgnBu2: Efficient Catalysts for Ring-Opening Polymerization of ε-Caprolactone and l-Lactide , 2004 .

[49]  M. Bochmann,et al.  Novel Zinc and Magnesium Alkyl and Amido Cations for Ring-Opening Polymerization Reactions , 2004 .

[50]  Y. Takashima,et al.  Bis(amido)titanium complexes having chelating diaryloxo ligands bridged by sulfur or methylene and their catalytic behaviors for ring-opening polymerization of cyclic esters , 2004 .

[51]  Zhiyuan Zhong,et al.  Single-Site Calcium Initiators for the Controlled Ring-Opening Polymerization of Lactides and Lactones , 2003 .

[52]  Ann-Christine Albertsson,et al.  Recent developments in ring opening polymerization of lactones for biomedical applications. , 2003, Biomacromolecules.

[53]  Bor-Hunn Huang,et al.  Aluminium metal complexes supported by amine bis-phenolate ligands as catalysts for ring-opening polymerization of ε-caprolactone , 2003 .

[54]  P. Degée,et al.  Mechanistic Study of Bu2SnCl2‐Mediated Ring‐Opening Polymerization of ε‐Caprolactone by Multinuclear NMR Spectroscopy , 2003 .

[55]  Guodong Zheng,et al.  Grafting of Poly(ε-caprolactone) and Poly(ε-caprolactone-block-(dimethylamino)ethyl methacrylate) from Polymer Microspheres by Ring-Opening Polymerization and ATRP , 2003 .

[56]  David R. Moore,et al.  Mechanism of the alternating copolymerization of epoxides and CO2 using beta-diiminate zinc catalysts: evidence for a bimetallic epoxide enchainment. , 2003, Journal of the American Chemical Society.

[57]  G. Jaouen,et al.  Synthesis and Structural Characterization of Neutral and Cationic Alkylaluminum Complexes Based on Bidentate Aminophenolate Ligands , 2003 .

[58]  M. Hillmyer,et al.  Electronic influence of ligand substituents on the rate of polymerization of ε-caprolactone by single-site aluminium alkoxide catalysts , 2003 .

[59]  P. Dubois,et al.  In situ formation of yttrium alkoxides: A versatile and efficient catalyst for the ROP of epsilon-caprolactone , 2003 .

[60]  M. Bochmann,et al.  Synthesis, Structures, and Ring-Opening Polymerization Reactions of Substituted Cyclopentadienyl Complexes of Zinc , 2003 .

[61]  D. Chakraborty,et al.  Chiral Amido Aluminum and Zinc Alkyls: A Synthetic, Structural, and Polymerization Study , 2003 .

[62]  Jwu-Ting Chen,et al.  Four- and five-coordinate aluminum ketiminate complexes: synthesis, characterization, and ring-opening polymerization. , 2002, Inorganic chemistry.

[63]  Mao-Lin Hsueh,et al.  Reactions of 2,2'-(2-methoxybenzylidene)bis(4-methyl-6-tert-butylphenol) with trimethylaluminum: Novel efficient catalysts for "living" and "immortal" polymerization of epsilon-caprolactone , 2002 .

[64]  M. Hillmyer,et al.  Mechanistic comparison of cyclic ester polymerizations by novel iron(III)-alkoxide complexes: single vs multiple site catalysis. , 2002, Journal of the American Chemical Society.

[65]  D. Chakraborty,et al.  Neutral, three-coordinate, chelating diamide aluminum complexes: Catalysts/initiators for synthesis of telechelic oligomers and high polymers , 2002 .

[66]  M. Okada.  Chemical syntheses of biodegradable polymers , 2002 .

[67]  D. Chakraborty,et al.  Neutral Olefin Polymerization Activators as Highly Active Catalysts for ROP of Heterocyclic Monomers and for Polymerization of Styrene , 2002 .

[68]  D. Navarro-Llobet,et al.  A Comparative Study in the Ring-Opening Polymerization of Lactides and Propylene Oxide , 2001 .

[69]  A. B. Huang,et al.  Reactions of 2,2‘-Methylenebis(4-chloro-6-isopropyl-3-methylphenol) with Trimethylaluminum: Highly Efficient Catalysts for the Ring-Opening Polymerization of Lactones , 2001 .

[70]  J. Feijen,et al.  A Novel and Versatile Calcium-Based Initiator System for the Ring-Opening Polymerization of Cyclic Esters , 2001 .

[71]  D. Navarro-Llobet,et al.  Molecular design of single site catalyst precursors for the ring-opening polymerization of cyclic ethers and esters. 2.1 Can ring-opening polymerization of propylene oxide occur by a cis-migratory mechanism? , 2001 .

[72]  J. Feijen,et al.  Calcium methoxide initiated ring-opening polymerization of ε-caprolactone and L-lactide , 2001 .

[73]  B. Ko,et al.  Ring-Opening Polymerization of ε-Caprolactone and l-Lactide Using Aluminum Thiolates as Initiator , 2001 .

[74]  M. Hillmyer,et al.  Polymerization of lactide and related cyclic esters by discrete metal complexes , 2001 .

[75]  M. Chisholm,et al.  Monomeric metal alkoxides and trialkyl siloxides: (BDI)Mg(OtBu)(THF) and (BDI)Zn(OSiPh3)(THF). Comments on single site catalysts for ring-opening polymerization of lactides , 2001 .

[76]  J. Hedrick,et al.  Sn(OTf)2 and Sc(OTf)3: Efficient and versatile catalysts for the controlled polymerization of lactones , 2000 .

[77]  A. Duda,et al.  Polymerization of l,l-Dilactide Initiated by Tin(II) Butoxide , 2000 .

[78]  D. Atwood,et al.  Bimetallic and cationic aluminum with N3O2 chelate ligands , 2000 .

[79]  P. Dubois,et al.  Controlled Ring-Opening Polymerization of ε-Caprolactone Promoted by “in Situ” Formed Yttrium Alkoxides , 2000 .

[80]  A. Duda,et al.  Mechanism of Cyclic Ester Polymerization Initiated with Tin(II) Octoate. 2.† Macromolecules Fitted with Tin(II) Alkoxide Species Observed Directly in MALDI−TOF Spectra , 2000 .

[81]  Roberto Solaro,et al.  Biodegradable Polymeric Materials , 1996 .

[82]  Toshio Hayashi,et al.  BIODEGRADABLE POLYMERS FOR BIOMEDICAL USES , 1994 .