The first-row transition metal catalysis often serves as a complementary strategy to traditional precious metal catalysis. Other than their advantages in abundance and sustainability, their unique electronic properties often give rise to more complicated reactivities. Co-catalyzed hydrogenation is an example of these relatively underexplored first-row transition metal catalysis. In this work, we will focus on an example of Co-catalyzed hydrogenation, which was reported to be able to selectively hydrogenate C=C but not C=O. We have performed DFT calculations on the model reactions, accompanied by a series of structure and bonding analysis, to investigate the underlying reason for the observed selectivity. We have identified the predominant σ-donating nature of phosphine and the π-accepting nature of C=C/C=O fragments upon interaction with Co(I) center, and we have also analyzed why these differences would lead to different coordination geometry, stability, and reactivity. We anticipate that all these analyses would advance our understanding in Co(I) catalysis and are beneficial for future Co-based catalyst design.

第一排过渡金属催化通常作为传统贵金属催化的补充策略。除了它们在丰富性和可持续性方面的优势外，它们独特的电子特性通常会引起更复杂的反应。共催化氢化是这些相对未充分探索的第一行过渡金属催化的一个例子。在这项工作中，我们将重点关注共催化氢化的一个例子，据报道它能够选择性氢化 C=C 但不能选择性氢化 C=O。我们对模型反应进行了 DFT 计算，并进行了一系列结构和键合分析，以研究观察到的选择性的根本原因。我们已经确定了膦的主要 σ 供体性质和 C=C/C=O 片段在与 Co(I) 中心相互作用时的 π 接受性质，并且我们还分析了为什么这些差异会导致不同的配位几何，稳定性和反应性。我们预计所有这些分析将增进我们对 Co(I) 催化的理解，并有利于未来的 Co 基催化剂设计。