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Volumn 133, Issue 23, 2011, Pages 9069-9087

Discrete, solvent-free alkaline-earth metal cations: Metal•• •fluorine interactions and ROP catalytic activity

Author keywords

[No Author keywords available]

Indexed keywords

BIOGRAPHIES; DYES; FLUORINE; INDIUM COMPOUNDS; LIGANDS; MAGNESIUM; METAL COMPLEXES; NEGATIVE IONS; POSITIVE IONS; RING OPENING POLYMERIZATION; SPECTROSCOPIC ANALYSIS; STRONTIUM; STRONTIUM COMPOUNDS; SYNTHESIS (CHEMICAL); X RAY CRYSTALLOGRAPHY; X RAY DIFFRACTION; ZINC;

EID: 79958839571     PISSN: 00027863     EISSN: 15205126     Source Type: Journal    
DOI: 10.1021/ja2024977     Document Type: Article
Times cited : (195)

References (208)
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    • 2 heteroleptic complexes (Ae = Ca, Sr, Ba); see ref 18h. The implementation of this method for the preparation of a broad range of heteroleptic Ae complexes is beyond the scope of the present study and will be the object of a separate report.
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    • The syntheses and characterization of 8 - 12 were reported in a preliminary account (33) and will not be discussed further here.
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    • n = 1.70), and the experimental molecular weight does not match its theoretical value. The polymerization in this case results either from a cationic mechanism, or from the presence of traces of protic impurities which act as initiator.
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    • 2 did not catalyse the polymerisation of L-LA.
    • 2 did not catalyse the polymerisation of L-LA.
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    • -0.352; see ref 16i.
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    • The limited temperature range was imposed by the boiling point of the solvent and the limited solubility of L-LA and PLLA in toluene at high concentration below 85 °C, which rendered the measurements inaccurate and non reproducible.
    • The limited temperature range was imposed by the boiling point of the solvent and the limited solubility of L-LA and PLLA in toluene at high concentration below 85 °C, which rendered the measurements inaccurate and non reproducible.
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    • 0 = 360:1:3.6), respectively. However, the accuracy of the measurements was limited in these cases, as we found that polymerization was often initiated before the first point of analysis (especially with 11 and 12) and that accurate determination of conversions was impeded by the poor solubilities of L-LA and especially PLLA at these temperatures. Owing to the high activity of complexes 10 - 12, higher polymerization temperatures to obtain homogeneous reaction mixtures were not suited as clearly the mechanism was not controlled in this case.
    • 0 = 360:1:3.6), respectively. However, the accuracy of the measurements was limited in these cases, as we found that polymerization was often initiated before the first point of analysis (especially with 11 and 12) and that accurate determination of conversions was impeded by the poor solubilities of L-LA and especially PLLA at these temperatures. Owing to the high activity of complexes 10 - 12, higher polymerization temperatures to obtain homogeneous reaction mixtures were not suited as clearly the mechanism was not controlled in this case.
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    • We have checked that with these systems, polymerization of L-LA does not occur under these conditions at room temperature except when complexes 8 or 9 are employed. In these two cases, polymerization prior to injection in the NMR probe can be inhibited by maintaining the NMR tube at low temperature.
    • We have checked that with these systems, polymerization of L-LA does not occur under these conditions at room temperature except when complexes 8 or 9 are employed. In these two cases, polymerization prior to injection in the NMR probe can be inhibited by maintaining the NMR tube at low temperature.
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