Reversible dissociation of H−X bond (M−L+H−X→M(X)-L(H); ) is an important step during pre-activation, catalysis and possible deactivation of acid-base cooperative pincer based transition metal catalysts (M−L). Herein we carried out a high-throughput computational investigation of the thermodynamic stability of different adducts in various functionalized Mn(I) based pincer complexes. We used a combination of density functional theory (DFT) and density functional tight binding (DFTB) calculations to analyze of >700 (M(X)-L(H)) intermediates based on functionalized variants of four pincer type ligand scaffolds derived from PCP, CNC, PNP and SNS ligands. We discovered linear scaling relations between of various species. Strongest correlations were found between species of similar size and chemical nature e. g. correlated best with and worst with . Such scaling relations can be useful for property based screening of catalysts and selection of (co)solvent/substrate/base for optimized reaction conditions. We also investigated the influence of the ligand backbone and the functionalization of donor and backbone sites in the ligand. Our analysis reveals the crucial role of the second coordination sphere functionalization for the reactivity of the complexes with impact in some cases exceeding that of the variation of the functional groups directly attached to the donor atoms.

中文翻译：

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HX (X=H, Br, OR) 键在锰基钳形配合物上的金属-配体协同活化

H-X 键的可逆解离 (M-L+H-X→M(X)-L(H); ) 是酸碱协同钳形过渡金属催化剂的预活化、催化和可能失活过程中的重要步骤(ML)。在此，我们对各种功能化的基于 Mn(I) 的钳形配合物中不同加合物的热力学稳定性进行了高通量计算研究。我们使用密度泛函理论 (DFT) 和密度泛函紧密结合 (DFTB) 计算的组合来分析基于来自 PCP 的四种钳型配体支架的功能化变体的 >700 (M(X)-L(H)) 中间体、CNC、PNP 和 SNS 配体。我们发现了之间的线性缩放关系的各种物种。在相似大小和化学性质的物种之间发现了最强的相关性 e。G。与 的最佳和最差相关 。这种比例关系可用于基于性质的催化剂筛选和（共）溶剂/底物/碱的选择以优化反应条件。我们还研究了配体骨架的影响以及配体中供体和骨架位点的功能化。我们的分析揭示了第二配位球官能化对配合物反应性的关键作用，在某些情况下影响超过直接连接到供体原子的官能团的变化。