The chemistry of bidentate ligands with a dppf-like motif, where phosphorus is fully or partially replaced by other pnictogens as donor sites, is summarized and discussed in this comprehensive review, while covering the literature from 1966 to 2024, related to more than 165 original references and discussing more than 75 independent chemical entities (1-41). Besides addressing synthetic, structural, and electrochemical aspects of such compounds, their donor properties and metal coordination behavior is discussed, along with catalytic applications. Based on their electronic and steric situations, trends in the performance of such compounds, either as ligands for catalysis or on their own merits for non-catalytic purposes, have been elucidated. Related topics that could not be covered in this article have been acknowledged by referring to the literature for completeness.
Keywords: amine; antimony; arsenic; bismuth; dppf-analogs; ferrocene; heteroditopic ligands; homoditopic ligands; pnictogens.