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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Ligand exchange upon oxidation of a dinuclear Mn complex-detection of structural changes by FT-IR spectroscopy and ESI-MS
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Ligand exchange upon oxidation of a dinuclear Mn complex-detection of structural changes by FT-IR spectroscopy and ESI-MS

机译：双核锰配合物氧化后的配体交换-通过FT-IR光谱和ESI-MS检测结构变化

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摘要

The structural rearrangements triggered by oxidation of the dinuclear Mn complex [Mn_2(bpmp)(mu-OAc)_2]~+ (bpmp = 2,6-bis[bis(2-pyridylmethyl)amino]methyl-4-methylphenol anion) in the presence of water have been studied by combinations of electrochemistry with IR spectroscopy and with electrospray ionization mass spectrometry (ESI-MS).The exchange of acetate bridges for water (D_2O) derived ligands in different oxidation states could be monitored by mid-IR spectroscopy in CD_3CN-D_2O mixtures following the v_(as(C-O)) bands of bound acetate at 1594.4 cm~(-1) (II,II),1592.0 cm~(-1) (II,III) and 1586.5 cm~(-1) (III,III).Substantial loss of bound acetate occurs at much lower water content (< 0.5% v/v) in the III,III state than in the II,II and II,III states (>=10%).The ligand-exchange reactions do not initially reduce the overall charge of the complex but facilitate further oxidation by proton-coupled electron transfer as the water-derived ligands are increasingly deprotonated in higher oxidation states.In the IR spectra deprotonation could be followed by the formation of acetic acid (DOAc,approx 1725 cm~(-1),v_(C-O)) from the released acetate (1573.6 cm~(-1),v_(as(C-O)).By the on-line combination of an electrochemical flow cell with ESI-MS several product complexes could be identified.A di-mu-oxo bridged III,IV dimer [Mn_2(bpmp)(mu-O)_2]~(2+) (m/z 335.8) can be generated at potentials below the III,III/II,III couple of the di-mu-acetato complex (0.61 V vs.ferrocene).The ligand-exchange reactions allow for three metal-centered oxidation steps to occur from II,II to III,IV in a potential range of only 0.5 V,explaining the formation of a spin-coupled III,IV dimer by photo-oxidation with [Ru[bpy)_3]~(3+) in previous EPR studies.
机译：由双核Mn络合物[Mn_2（bpmp）（mu-OAc）_2]〜+（bpmp = 2,6-双[双（2-吡啶基甲基）氨基]甲基-4-甲基苯酚阴离子）氧化引发的结构重排。通过电化学，红外光谱和电喷雾电离质谱（ESI-MS）的组合研究了水的存在。中红外光谱可监测乙酸桥与水（D_2O）衍生的配体在不同氧化态下的交换在1594.4 cm〜（-1）（II，II），1592.0 cm〜（-1）（II，III）和1586.5 cm〜（-）上结合乙酸盐的v_（as（CO））带跟随CD_3CN-D_2O混合物1）（III，III）。与II，II和II，III状态（> = 10％）相比，III，III状态的水分含量低得多（<0.5％v / v）时，结合的乙酸盐大量损失配体交换反应最初不会降低复合物的总电荷，但会随着水衍生的配体在较高o在红外光谱中，去质子化后可能是从释放的乙酸盐（1573.6 cm〜（-1），v_（as）形成乙酸（DOAc，约1725 cm〜（-1），v_（CO））。 （CO））。通过电化学流动池与ESI-MS的在线结合，可以鉴定出几种产物配合物。二-μ-氧代桥联的III，IV二聚体[Mn_2（bpmp）（mu-O）_2] 〜（2+）（m / z 335.8）可以在di-mu-acetato络合物的III，III / II，III对以下（0.61 V vs.二茂铁）下产生。配体交换反应可实现三个从II，II到III，IV的金属中心氧化步骤仅在0.5 V的电位范围内发生，解释了通过[Ru [bpy）_3]〜（光氧化形成自旋耦合的III，IV二聚体3+）在以前的EPR研究中。

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