Metal–metal bond distances and bond orders in dimanganese complexes with bidentate ligands: scope for some very short Mn–Mn bonds,New Journal of Chemistry

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Metal–metal bond distances and bond orders in dimanganese complexes with bidentate ligands: scope for some very short Mn–Mn bonds
New Journal of Chemistry ( IF 2.7 ) Pub Date : 2020-07-13 , DOI: 10.1039/d0nj01305f
Fitzerald Hujon _{1,

2,

3,

4} , R. H. Duncan Lyngdoh _{1,

2,

3,

4,

5} , R. Bruce King _{5,

6,

7,

8}

Affiliation

Binuclear manganese complexes with covalent Mn–Mn bonds include dimanganese carbonyl complexes and dimanganese non-carbonyl complexes with bidentate anionic ligands. Density functional theory (DFT) using the M06-L functional is used to study some known dimanganese complexes and three series of model paddlewheel-type dimanganese complexes M₂L_x and M₂L_x·2H₂O (L = HNCHNH, HNC(NH₂)NH and OCHO respectively; x = 2, 3, 4). The DFT results for model structures for known dimanganese complexes agree well with the experimental structures and lead to predictions of ground state spin multiplicities. For the model paddlewheel-type complexes, predictions are made with regard to ground state spin multiplicities, and Mn–Mn bond lengths. Formal bond orders (fBO) from 0.5 to 4.5 for all the Mn–Mn bonds are assigned by electron counting. Molecular orbital analysis yields Mn–Mn bond orders (BO) matching the fBO values. Four “super-short” Mn–Mn bonds (lengths 1.618 to 1.639 Å) are found in higher energy isomers, along with other short Mn–Mn quadruple bonds. The effects of axial ligation by two H₂O ligands are also noted. The Mn–Mn bond lengths are categorized into distinct ranges as per the Mn–Mn fBO values from 0.5 to 4.5, ranges which are compared with other experimental and computational estimates.

中文翻译：

具有二齿配体的二锰配合物中金属-金属键的距离和键序：一些非常短的Mn-Mn键的范围

具有共价Mn-Mn键的双核锰配合物包括二锰羰基配合物和具有二齿阴离子配体的二锰非羰基配合物。使用M06-L官能团的密度泛函理论（DFT）研究了一些已知的二锰配合物和三个系列的桨轮型二锰配合物M ₂ L _x和M ₂ L _x ·2H ₂ O（L = HNCHNH，HNC（ NH ₂）NH和OCHO分别; x= 2、3、4）。已知二锰配合物的模型结构的DFT结果与实验结构非常吻合，并导致对基态自旋多重性的预测。对于模型桨轮型配合物，对基态自旋多重性和Mn-Mn键长进行了预测。所有Mn-Mn键的形式键序（fBO）从0.5到4.5通过电子计数分配。分子轨道分析得出与fBO值匹配的Mn–Mn键序（BO）。在高能异构体中发现了四个“超短” Mn-Mn键（长度为1.618至1.639Å），以及其他短的Mn-Mn四重键。两个H ₂轴向结扎的影响还指出了O配体。根据Mn-Mn fBO值（从0.5到4.5），将Mn-Mn键长分为不同的范围，并与其他实验和计算估计值进行比较。

更新日期：2020-08-03

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