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• W2019346344 endingPage "4987" @default.
• W2019346344 startingPage "4977" @default.
• W2019346344 abstract "Five-coordinate manganese(III) complexes of N, N'-bis(trifluoroacetylacetone)-1,2-ethylenediimine (tfacacen) have been synthesized and structurally characterized by X-ray crystallography. The presence of the electron-withdrawing -CF3 substituents enhances the electrophilicity of the metal center in these (tfacacen)MnX (X=Cl, N3, NCO, NCS) derivatives when compared with their (acacen)MnX (acacen=N, N'-bis(acetylacetone)-1,2-ethylenediimine) analogs. This is demonstrated by the increased propensity of the Mn(III) center in the tfacacen complexes to bind a sixth ligand. Binding studies were performed utilizing the upsilonN3 stretching frequency in (tfacacen)MnN3, which is sensitive to the coordination of a ligand at the vacant axial site. Of importance, cyclohexene oxide was shown to readily bind to (tfacacen)MnN3, thereby providing an opportunity for directly monitoring the dependence of the epoxide ring-opening process on the metal complex concentration. In this instance, as has been amply demonstrated in the (salen)CrX case, the ring opening of cyclohexene oxide was found to be second-order in [(tfacacen)MnN3], with an activation energy of 71.0+/-6.0 kJ/mol. In the presence of strongly coordinating anions or amine bases, the rate of epoxide ring opening by (tfacacen)MnN3 was greatly retarded. The manganese cyanate and thiocyanate complexes were examined in an effort to develop other initiators for epoxide ring opening which provide readily accessible infrared spectroscopic probes. Indeed, the thiocyanate ligand was found to be well-suited for monitoring the epoxide ring-opening reaction by infrared spectroscopy." @default.
• W2019346344 created "2016-06-24" @default.
• W2019346344 creator A5036575620 @default.
• W2019346344 creator A5077255739 @default.
• W2019346344 date "2008-04-26" @default.
• W2019346344 modified "2023-10-16" @default.
• W2019346344 title "Studies of the Carbon Dioxide and Epoxide Coupling Reaction in the Presence of Fluorinated Manganese(III) Acacen Complexes: Kinetics of Epoxide Ring-Opening" @default.
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• W2019346344 doi "https://doi.org/10.1021/ic800286p" @default.
• W2019346344 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/18439001" @default.
• W2019346344 hasPublicationYear "2008" @default.
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