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N2 Reduction on Fe‐Based Complexes with Different Supporting Main‐Group Elements: Critical Roles of Anchor and Peripheral Ligands
Small Methods ( IF 10.7 ) Pub Date : 2018-10-17 , DOI: 10.1002/smtd.201800340 Ya‐Fei Jiang 1 , Xue‐Lu Ma 1, 2 , Jun‐Bo Lu 1 , Jia‐Qi Wang 1 , Hai Xiao 1 , Jun Li 1
Small Methods ( IF 10.7 ) Pub Date : 2018-10-17 , DOI: 10.1002/smtd.201800340 Ya‐Fei Jiang 1 , Xue‐Lu Ma 1, 2 , Jun‐Bo Lu 1 , Jia‐Qi Wang 1 , Hai Xiao 1 , Jun Li 1
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Due to the enigmatic existence of the carbon atom in the MoFeS cluster of iron‐molybdenum cofactor (FeMoco), the design of biomimetic model catalysts featuring a dative bond between a transition metal and a main group atom is an important topic for efficient reduction of N2 to NH3 at ambient conditions. Different anchor atoms (X) for the trigonal bipyramidal (XPiPr
3)Fe (X = B, C, N) catalyst scaffold are investigated by theory. The calculations show that from Lewis acidic B anchor to Lewis basic N or P anchor, the molecular orbital energy levels consisting mainly of Fe 3d orbitals are pushed higher, thus causing stronger backdonation bonding with the π* orbitals of N2, which promotes activation of N2 but impedes reduction of N2. The redox‐flexible bonding can act as an electron reservoir and buffer the oxidation state variation of Fe. However, when the FeX bond is less flexible, the peripheral ligands can serve as an extra electron reservoir in the model with Lewis basic anchor. Thus, engineering the peripheral ligand with proper electron‐withdrawing substituent groups can promote reduction of N2. The ability to balance well the electron‐donating ability of anchor and electrophilicity of the peripheral ligand is a promising direction toward novel efficient catalysts for N2 fixation.
中文翻译：
具有不同支持主族元素的铁基配合物的N2还原：锚和周边配体的关键作用
由于沫中的碳原子的神秘存在铁铁-钼辅因子（FeMoco）的S簇，具有过渡金属和主族原子之间的配位键仿生模型催化剂的设计是一个重要的课题在环境条件下将N 2有效还原为NH 3。通过理论研究了三角双锥体（XP iPr 3）Fe（X = B，C，N）催化剂支架的不同锚原子（X）。计算表明，从路易斯酸性B锚到路易斯碱性N或P锚，主要由Fe 3d轨道组成的分子轨道能级被推高，从而导致与N的π*轨道更强的背键键合。2，其促进N 2的活化但阻碍N 2的还原。氧化还原-挠性键可以充当电子存储库，并缓冲Fe的氧化态变化。但是，当FeX键的柔韧性较低时，外围配体可以在具有Lewis碱性锚的模型中充当额外的电子储库。因此，用适当的吸电子取代基改造外围配体可以促进N 2的还原。良好地平衡锚的供电子能力和周围配体的亲电性的能力是朝着新型的高效N 2固定催化剂发展的有前途的方向。
更新日期：2018-10-17
中文翻译：
具有不同支持主族元素的铁基配合物的N2还原：锚和周边配体的关键作用
由于沫中的碳原子的神秘存在铁铁-钼辅因子（FeMoco）的S簇，具有过渡金属和主族原子之间的配位键仿生模型催化剂的设计是一个重要的课题在环境条件下将N 2有效还原为NH 3。通过理论研究了三角双锥体（XP iPr 3）Fe（X = B，C，N）催化剂支架的不同锚原子（X）。计算表明，从路易斯酸性B锚到路易斯碱性N或P锚，主要由Fe 3d轨道组成的分子轨道能级被推高，从而导致与N的π*轨道更强的背键键合。2，其促进N 2的活化但阻碍N 2的还原。氧化还原-挠性键可以充当电子存储库，并缓冲Fe的氧化态变化。但是，当FeX键的柔韧性较低时，外围配体可以在具有Lewis碱性锚的模型中充当额外的电子储库。因此，用适当的吸电子取代基改造外围配体可以促进N 2的还原。良好地平衡锚的供电子能力和周围配体的亲电性的能力是朝着新型的高效N 2固定催化剂发展的有前途的方向。
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