Further investigation of the ring-opening polymerization of propylene oxide. Catecholate derivatives of Zn(II) and Al(III)

Chisholm, Malcolm H.; Gallucci, Judith C.; Navarro-Llobet, Diana; Zhen, Hongshi

doi:10.1016/s0277-5387(02)01414-6

Cited by 16 publications

(10 citation statements)

References 25 publications

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“…It is easy to envisage this metal-assisted mechanism operating in a bimetallic manner as shown in Scheme 2. 45 Many of the early catalyst systems developed were heterogeneous, e.g. ZnEt 2 / H 2 O and the calcium amide/alkoxide system of Union Carbide, 42,[46][47][48][49] and consequently little is actually known about the intimate mechanism.…”

Section: Polyether Production From Epoxides: Ring-opening Polymerizat...mentioning

confidence: 99%

New generation polymers: the role of metal alkoxides as catalysts in the production of polyoxygenates

2004

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Section: Polyether Production From Epoxides: Ring-opening Polymerizat...mentioning

confidence: 99%

New generation polymers: the role of metal alkoxides as catalysts in the production of polyoxygenates

2004

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“…8,[26][27][28][29][30][31] This report details the extension of this strategy to the coordination complexes of aluminum, which are dominated by the Al(III) oxidation state. Previous studies of redox-active ligands on aluminum(III) include, homoleptic Al[ONO] 2 and Al(SQ) 3 complexes (SQ = semiquinonate form of a bidentate catecholate ligand), 14,15,32,33 as well as several intriguing aluminum(III) complexes containing redoxactive iminopyridine ligands. [34][35][36] Herein, we report the synthesis and preliminary characterization of a series of aluminum(III) complexes containing a single [ONO] ligand.…”

Section: Introductionmentioning

confidence: 99%

Aluminum complexes of the redox-active [ONO] pincer ligand

Szigethy

Heyduk

2012

Dalton Trans.

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A series of aluminum complexes containing the tridentate, redox-active ligand bis(3,5-di-tert-butyl-2-phenol)amine ([ONO]H(3)) in three different oxidation states were synthesized. The aluminum halide salts AlCl(3) and AlBr(3) were reacted with the doubly deprotonated form of the ligand to afford five-coordinate [ONHO(cat)]AlX(solv) complexes (1a, X = Cl, solv = OEt(2); 1b, X = Br, solv = THF), each having a trigonal bipyramidal coordination geometry at the aluminum and containing the [ONHO(cat)](2-) ligand with a protonated, sp(3)-hybridized nitrogen donor. The [ONO] ligand platform may also be added to aluminum through the use of the oxidized ligand salt [ONO(q)]K, which was reacted with AlCl(3) in the presence of either diphenylacetylacetonate (acacPh(2)(-)) or 8-oxyquinoline (quinO(-)) to afford [ONO(q)]Al(acacPh(2))Cl (2) or [ONO(q)]Al(quinO)Cl (3), respectively, with well-defined [ONO(q)](-) ligands. Quinonate complexes 2 and 3 were reduced by one electron to afford the corresponding complexes K{[ONO(sq)]Al(acacPh(2))(py)} (4) and K{[ONO(sq)]Al(quinO)(py)} (5), respectively, containing well-defined [ONO(sq)](2-) ligands. The addition of tetrachloro-1,2-quinone to 1a in the presence of pyridine resulted in the expulsion of HCl and the formation of an aluminum complex with two different redox active ligands, [ONO]Al(o-O(2)C(6)Cl(4))(py) (6). Similar results were obtained when 1a was reacted with 9,10-phenanthrenequinone to afford [ONO]Al(o-O(2)C(14)H(8))(py) (7) or with pyrene-4,5-dione to afford [ONO]Al(o-O(2)C(16)H(8))(py) (8). Structural, spectroscopic and preliminary magnetic measurements on 6-8 suggest ligand non-innocent redox behavior in these complexes.

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“…[8][9][10][11][12][13][14] In addition, aluminum alkoxide derivatives have proven to be very efficient catalysts in many polymerization reactions, such as ring-opening polymerization. [15][16][17][18][19][20] The appeal of aluminum is complemented by a rich structural chemistry; thus aluminum derivatives of a vast nuclearity range have been described. [21][22][23][24][25][26][27][28] In this note we report the synthesis and structural characterization of new aluminum aryloxide complexes.…”

Section: Introductionmentioning

confidence: 99%

Controlled Synthesis of Novel Aryloxide Polynuclear Aluminum Species. Study of Their Catalytic Properties in Polymerization Processes

et al. 2008

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The reaction of AlMe 3 with 3,5-(CF 3 ) 2 C 6 H 3 OH at room temperature renders the dinuclear [AlMe 3) derivative depending on the reaction conditions (solvent and stoichiometry of the reagents). All compounds have been characterized by elemental analysis and NMR spectroscopy, and their crystal structures determined by X-ray diffraction methods. Catalytic studies reveal that these compounds show high activity in ring-opening polymerization of cyclohexene oxide (CHO). The activity in the catalytic process varies significantly with solvent and temperature conditions.

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Further investigation of the ring-opening polymerization of propylene oxide. Catecholate derivatives of Zn(II) and Al(III)

Cited by 16 publications

References 25 publications

New generation polymers: the role of metal alkoxides as catalysts in the production of polyoxygenates

New generation polymers: the role of metal alkoxides as catalysts in the production of polyoxygenates

Aluminum complexes of the redox-active [ONO] pincer ligand

Controlled Synthesis of Novel Aryloxide Polynuclear Aluminum Species. Study of Their Catalytic Properties in Polymerization Processes

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