The catalytic functionalization of light alkanes, particularly methane, has attracted considerable attention from the inorganic and organic research communities for nearly five decades. The literature mechanisms for C—H activation may be divided into three broad categories: metal directed, ligand directed, or metal-ligand directed. The advantages for metal-ligand directed pathways have both steric and electronic origins. Furthermore, computations suggest that the stereoelectronic requirements for the activation and functionalization component reactions can be diametrically opposed. From this research, several questions emerge for theorists that would aid in the hunt for synthesizable complexes for efficient catalytic functionalization of light alkanes. First, is there a happy medium by which a complex is nucleophilic enough to activate a alkane C—H bond with a reasonable rate, but that is not so basic as to thwart the subsequent C—O,N bond-forming step? Second, what are the energetic consequences of moving along the “ide”/“yl” continuum? Third, how can the electronic coupling among the three main catalyst components—metal, actor ligand, and spectator ligand—be modulated to permit the use of Earth-abundant catalysts to effect catalytic functionalization of light alkanes?

轻链烷烃，特别是甲烷的催化功能化，近五十年来一直受到无机和有机研究界的广泛关注。用于CH活化的文献机制可分为三大类：金属定向，配体定向或金属配体定向。金属-配体定向途径的优点具有空间和电子起源。此外，计算表明激活和官能化组分反应的立体电子要求可以完全相反。从这项研究中，理论家提出了几个问题，这些问题将有助于寻找可合成的络合物，以有效地催化轻烷烃。第一，有没有一种令人满意的媒介物，可以使配合物具有足够的亲核性，从而以合理的速率激活烷烃CH键，但是这种方法的基本性不足以阻止后续的CHN键形成步骤？第二，沿着“ ide” /“ yl”连续体移动会产生什么能量后果？第三，如何调节三种主要催化剂成分（金属，演员配体和观众配体）之间的电子偶联，以允许使用地球富集的催化剂来实现轻链烷烃的催化功能化？