1,2-Bis(diphenylphosphino)ethane (DPPE) and its synthetic analogues are important structural motifs in organic synthesis, particularly as diphosphine ligands with a C₂-alkyl-linker chain. Since DPPE is known to bind to many metal centers in a bidentate fashion to stabilize the corresponding metal complex via the chelation effect originating from its entropic advantage over monodentate ligands, it is often used in transition-metal-catalyzed transformations. Symmetric DPPE derivatives (Ar¹₂P−CH₂−CH₂−PAr¹₂) are well-known and readily prepared, but electronically and sterically unsymmetric DPPE (Ar¹₂P−CH₂−CH₂−PAr²₂; Ar¹≠Ar²) ligands have been less explored, mostly due to the difficulties associated with their preparation. Here we report a synthetic method for both symmetric and unsymmetric DPPEs via radical difunctionalization of ethylene, a fundamental C₂ unit, with two phosphine-centered radicals, which is guided by the computational analysis with the artificial force induced reaction (AFIR) method, a quantum chemical calculation-based automated reaction path search tool. The obtained unsymmetric DPPE ligands can coordinate to several transition-metal salts to form the corresponding complexes, one of which exhibits distinctly different characteristics than the corresponding symmetric DPPE–metal complex.

1,2-双（二苯基膦基）乙烷 (DPPE) 及其合成类似物是有机合成中的重要结构基序，特别是作为具有 C ₂ -烷基连接链的二膦配体。由于已知 DPPE 以双齿方式与许多金属中心结合，通过源自其相对于单齿配体的熵优势的螯合效应稳定相应的金属络合物，因此它通常用于过渡金属催化的转化。对称的 DPPE 衍生物 (Ar ¹ ₂ P−CH ₂ −CH ₂ −PAr ¹ ₂ ) 是众所周知且易于制备的，但电子和空间不对称的 DPPE (Ar ¹ ₂ P−CH ₂ −CH ₂-PAr ² ₂ ; Ar ¹ ≠Ar ² ) 配体的探索较少，主要是由于与其制备相关的困难。在这里，我们报告了一种通过乙烯的自由基双官能化合成对称和不对称 DPPE 的方法，乙烯是一个基本的 C ₂单元，具有两个以膦为中心的自由基，该方法以人工力诱导反应 (AFIR) 方法的计算分析为指导，基于量子化学计算的自动化反应路径搜索工具。获得的不对称 DPPE 配体可以与几种过渡金属盐配位形成相应的配合物，其中一种表现出与相应的对称 DPPE-金属配合物明显不同的特性。