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首页> 外文期刊>Chemistry: A European journal >The Impact of Surfactants on Felli—TAML-Catalyzed Oxidations byPeroxides: Accelerations, Decelerations, and Loss of Activity
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The Impact of Surfactants on Felli—TAML-Catalyzed Oxidations byPeroxides: Accelerations, Decelerations, and Loss of Activity

机译：表面活性剂对Felli-TAML催化的过氧化物氧化的影响：加速，减慢和活性降低

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摘要

Iron(III) complexes of tet-raamicittomacrocyclicligands (TAMLs), [Fe{4-XC6H3-1,2-(NCOCMe2NC0)2CR2}(OH2)] 1 (la:X--H, R=Me; lb: X=COOH, R=Me); lc: X = CONH(CH2)2COOH,R =Me; 1d: CONH(CH2)2NMe2, R=Me; le: X = CONH(CH2)2NMe3±, R=Me; I f: X=H, R=F), have beentested as catalysts for the oxidative de-colorization of Orange II and Sudan IIIdyes by hydrogen peroxide and tert-butyl hydroperoxide in the presence ofmicelles that are neutral (Triton X-100), positively charged (cetyltrimethyl-ammonium bromide, CTAB), and neg-atively charged (sodium dodecyl sul-fate, SDS). The previously reportedmechanism of catalysis involves the for-mation of an oxidized intermediate from 1 and ROOH (k1) followed bydye bleaching (k11). The micellar effectson k1 and k11 have been separately stud-ied and analyzed by using the Berezinpseudophase model of micellar cataly-sis. The largest micellar acceleration interms of k1 occurs for the 1 a-tBuO0H—CTAB system. At pH 9.0-10.5 the rate constant k1 increased byapproximately five times with increas-ing CTAB concentration and thengradually decreased. There was no ac-celeration at higher pH, presumablyowing to the deprotonation of the axialwater ligand of la in this pH range.
机译：tet-raamicittomacrocyclicligands（TAMLs）[[Fe {4-XC6H3-1,2-（NCOCMe2NC0）2CR2}（OH2）] 1的铁（III）络合物（la：X--H，R = Me; lb：X = COOH，R ＝ Me）; lc：X ＝ CONH（CH 2）2 COOH，R ＝ Me; 1d：CONH（CH2）2NMe2，R = Me; le：X ＝ CONH（CH 2）2 NMe 3±，R ＝ Me; I f：X = H，R = F）已作为中性胶束（Triton X-100）在过氧化氢和叔丁基氢过氧化物的作用下作为橙色II和苏丹III染料氧化脱色的催化剂，带正电的（十六烷基三甲基溴化铵，CTAB）和带负电的（十二烷基硫酸钠，SDS）。先前报道的催化机理涉及从1和ROOH（k1）形成氧化中间体，然后进行染料漂白（k11）。通过使用胶束催化的贝雷津假相模型分别研究和分析了对k1和k11的胶束效应。对于1 a-tBuO0H-CTAB系统，最大的胶束加速度项k1出现。在pH 9.0-10.5时，速率常数k1随着CTAB浓度的增加而增加约五倍，然后逐渐降低。推测是由于在此pH范围内la的轴向水配体的去质子作用，因此在较高的pH下没有加速作用。

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