Two mixed-valence Mn(II)Mn(III) complexes, [Mn₂L¹(OAc)₂(H₂O)]BPh₄·2.5H₂O and [Mn₂L²(OAc)₂]·4H₂O, obtained with unsymmetrical N₄O₂-hexadentate L¹⁽²⁻⁾ (H₂L¹ = 2-(N,N-bis(2-(pyridylmethyl)aminomethyl)-6-(N-(2-hydroxybenzyl)benzylaminomethyl)-4-methylphenol) and N₄O₃-heptadentate L²⁽³⁻⁾ (NaH₂L² = 2-(N,N-bis(2-(pyridylmethyl)aminomethyl)-6-(N′-(2-hydroxybenzyl)(carboxymethyl)aminomethyl)-4-methylphenol sodium salt) ligands, have been prepared and characterized. Both complexes share a μ-phenolate-bis(μ-acetate)Mn(II)Mn(III) core and N₃O₃-coordination sphere around the Mn(II) ion, but differ in the donor groups surrounding Mn(III) (NO₄(solvent) and NO₅). In non-protic solvents, these two complexes are able to disproportionate at least 3600 equiv. of H₂O₂ without significant decomposition, with first-order dependence on catalyst and saturation kinetics on [H₂O₂]. Spectroscopic monitoring of the reaction mixtures revealed the two complexes disproportionate H₂O₂ employing a different redox cycle, with retention of dinuclearity. The higher catalytic efficiency of [Mn₂L²(OAc)₂] was rationalized in terms of the larger labilizing effect of the heptadentate ligand that favors the acetate-shift and the replacement of the non-coordinating benzyl arm of L¹ by a carboxylate arm in L² which facilitates the formation of the catalyst-H₂O₂ adduct, placing [Mn₂L²(OAc)₂] as the most efficient among the phenolate-bridged diMn catalysts based on the k_cat/K_M criterion.

两种混合价的Mn（II）Mn（III）络合物，[Mn ₂ L ¹（OAc）₂（H ₂ O）] BPh ₄ ·2.5H ₂ O和[Mn ₂ L ²（OAc）₂ ]·4H ₂由不对称的N ₄ O _2-六齿L ^1（2-）（H ₂ L ¹  = 2-（N，N-双（2-（吡啶基甲基）氨基甲基）-6-（N-（2-羟基苄基））苄基氨基甲基）-4-甲基苯酚）和N ₄ O ₃七齿L ^2（3-）（NaH ₂ L制备并表征了²  ＝ 2-（N，N-双（2-（吡啶基甲基）氨基甲基）-6-（N'-（2-羟基苄基）（羧甲基）氨基甲基）-4-甲基苯酚钠盐）的配体。两种配合物在Mn（II）离子周围共享一个μ-酚盐-双（μ-乙酸盐）Mn（II）Mn（III）核和N ₃ O _3-配位球，但在Mn（III）周围的供体基团上有所不同（NO ₄（溶剂）和NO ₅）。在非质子溶剂中，这两种络合物能够歧化至少3600当量。H ₂ O _2的分解没有显着分解，对催化剂的一级依赖性和对[H₂ O ₂ ]。对反应混合物的光谱监控显示，采用不同的氧化还原循环，保留了双核，这两种配合物的H ₂ O ₂不成比例。考虑到七齿配体的更大的有力化作用，这有助于提高[Mn ₂ L ²（OAc）₂ ]的催化效率，有利于乙酸盐转移和L ¹的非配位苄基臂被羧酸盐取代L ²中的臂，有助于形成催化剂-H ₂ O ₂加合物，并放置[Mn ₂ L ²（OAc）₂在基于k _cat / K _M准则的酚盐桥接的DiMn催化剂中，这是最有效的。