کد مقاله | کد نشریه | سال انتشار | مقاله انگلیسی | نسخه تمام متن |
---|---|---|---|---|
1304084 | 1498970 | 2012 | 5 صفحه PDF | دانلود رایگان |
![عکس صفحه اول مقاله: Low temperature reaction of [Fe(TPA)(CH3CN)2]2+ with excess 3-chloroperoxybenzoic acid in semi-frozen acetonitrile; EPR detection of an acylperoxo iron(III) adduct Low temperature reaction of [Fe(TPA)(CH3CN)2]2+ with excess 3-chloroperoxybenzoic acid in semi-frozen acetonitrile; EPR detection of an acylperoxo iron(III) adduct](/preview/png/1304084.png)
Treatment of [(TPA)FeII(CH3CN)2]2+ (TPA = tris(2-pyridylmethyl)amine) with excess (≥ 2 Eq) of 3-chloroperoxybenzoic acid (mCPBA) in semi-frozen acetonitrile in liquid N2 vapour generates a rhombic EPR signal assigned to the S = ½ low spin acylperoxoiron(III) species [(TPA)Fe(O3CC6H4-3Cl)(CH3CN)]2+5; the elusive precursor on the pathway to [(TPA)FeIII(5-chlorosalicylate)]+4 via putative [(TPA)FeV(O)(O2CC6H4-3Cl)]2+. Formation of cyclohexene epoxide in the presence of added cyclohexene at low temperatures (<−40 °C) suggests that intermolecular alkene epoxidation competes successfully with the intramolecular reactions involving 5 to generate 4.
Treatment of [(TPA)Fe(CH3CN)2]2+1 with excess (≥ 2 Eq) of 3-chloroperoxybenzoic acid (mCPBA) in semi-frozen acetonitrile generates an S = ½ EPR signal assigned to the low spin acylperoxo iron(III) species; [(TPA)Fe(O3CC6H4-3Cl)(CH3CN)]2+5; the elusive precursor to putative ‘(TPA)FeV(O)’ on the pathway to [(TPA)FeIII(5-chlorosalicylate)]+. Solutions of 5 are also active in promoting cyclohexene epoxidation.Figure optionsDownload as PowerPoint slideHighlights
► Mixing [(TPA)FeII(CH3CN)2]2+ with ≥2eq mCPBA in semi-frozen acetonitrile forms [(TPA)Fe(O3CC6H4-3Cl)(CH3CN)]2+5.
► Detection (by EPR) of 5 for the first time is as a result of mixing the reagents in the semi-frozen acetonitrile medium.
► 5 is the direct precursor of putative ‘(TPA)FeV(O)2+’ on the pathway to [(TPA)FeIII(5-Cl-salicylate)]+, the final product.
► Generation of cyclohexene epoxide shows that intermolecular alkene epoxidation competes with intramolecular CH O-insertion.
► The findings cannot rule out the possibility that acylperoxoiron(III) complexes can themselves promote alkene epoxidation.
Journal: Inorganic Chemistry Communications - Volume 20, June 2012, Pages 81–85