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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Exploring the effect of the Ln(III)/Ln(II) redox potential on C-F activation and on oxidation of some lanthanoid organoamides
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Exploring the effect of the Ln(III)/Ln(II) redox potential on C-F activation and on oxidation of some lanthanoid organoamides

机译：探索Ln（III）/ Ln（II）氧化还原电势对C-F活化和某些镧系元素有机酰胺的氧化的影响

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The divalent europium complexes, [Eu(L-Me/Et)(2)(thf)(2)] and [Eu(L-Et)(2)(dme)] (L-Me/Et = p-HC6F4N(CH2)(2)NMe2/Et-2), have been prepared from redox-transmetallation/protolysis (RTP) reactions between Eu metal, Hg(C6F5)(2) and (LH)-H-Me/Et in thf. The complexes exhibit close (C)F-Ln interactions and the amide ligands feature tridentate N,N',F chelation. The complexes are thermally robust but on exposure to light they undergo C-F activation. From exposure of [Eu(L-Et)(2)(thf)(2)] to light, the E-III mixed fluoride/oxide cluster, [Eu-4(L-Et)(6)F2O2] was isolated, but other well-defined C-F activation products have proven elusive due to the stability of Eu-II. Oxidation of [Ln(L-R)(2)(thf)(2)] (Ln = Eu, R = Me; Ln = Yb, R = Et) with I-2 afforded the heteroleptic iodo complexes, [Ln(L-R)(2)(thf)(n)] (Ln = Eu, n = 1; Ln = Yb, n = 0), and the homoleptic complexes, [Ln(LR)(3)]. The formation of the iodo complexes and the heteroleptic complexes appear to occur by different routes. [Yb(La)(3)] shows interesting structural differences from reported Ln(L-Et)(3)] (Ln = La, Ce, Nd) complexes, and highlights an incomplete shift towards N,N' chelation to the much smaller Yb ion. [Sm(Lme)(3)] was prepared from a protolysis reaction between [Sm(CH2C6H,-NMe2-o)(3)] and LmeH. Heating a solution of [Sm(Lme)(3)] in toluene at 110 degrees C for three days did not afford any samarium fluoride complex. An RTP reaction with Sm afforded the heteroleptic samarium complex, [Sm(L-Me)(2)F](3), in very low yield. From an attempted protolysis reaction between 1Sm(DippForm)(2)(thf)(2)] and LmTh, the mixed ligand samarium fluoride complex, [Sm(DippForm)(L-me)F]n(2), was isolated. Overall, the instability of Sm-II precludes control over the C-F activation reactions.
机译：二价euro络合物[Eu（L-Me / Et）（2）（thf）（2）]和[Eu（L-Et）（2）（dme）]（L-Me / Et = p-HC6F4N（ CH2）（2）NMe2 / Et-2）是由Eu金属，Hg（C6F5）（2）和（LH）-H-Me / Et之间的氧化还原-金属转移/质子分解（RTP）反应制得的。该配合物表现出紧密的（C）F-Ln相互作用，并且酰胺配体具有三齿的N，N′，F螯合。该配合物具有耐热性，但是在暴露于光线下会经历C-F活化。从[Eu（L-Et）（2）（thf）（2）]曝光后，分离出E-III混合的氟化物/氧化物簇[Eu-4（L-Et）（6）F2O2]，但是由于Eu-II的稳定性，其他定义明确的CF活化产物已被证明难以捉摸。用I-2氧化[Ln（LR）（2）（thf）（2）]（Ln = Eu，R = Me; Ln = Yb，R = Et）得到杂配碘配合物[Ln（LR）（ 2）（thf）（n）]（Ln = Eu，n = 1; Ln = Yb，n = 0），以及纯合络合物[Ln（LR）（3）]。碘配合物和杂配物的形成似乎是通过不同的途径发生的。 [Yb（La）（3）]与报道的Ln（L-Et）（3）表现出有趣的结构差异（Ln = La，Ce，Nd），并强调了向N，N'螯合的不完全转移较小的Yb离子。 [Sm（Lme）（3）]由[Sm（CH2C6H，-NMe2-o）（3）]和LmeH之间的质子分解反应制备。将[Sm（Lme）（3）]在甲苯中的溶液在110摄氏度下加热三天，没有得到任何氟化mar络合物。与Sm的RTP反应以非常低的产率提供了杂配l络合物[Sm（L-Me）（2）F]（3）。从尝试的1Sm（DippForm）（2）（thf）（2）和LmTh的蛋白水解反应中，分离出混合配体氟化sa络合物[Sm（DippForm）（L-me）F] n（2）。总体而言，Sm-II的不稳定性使得无法控制C-F活化反应。

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