Abstract
• Developments of the chemistry of bulky dppf analogs over the past four decades have been reviewed. • Strategies for their preparation and transformation have been outlined. • Spectroscopic and electrochemical consequences of increasing steric bulk have been summarized. • A survey of the catalytic properties is given and summarized. • Perspectives for future research activities of bulky dppf analogs are briefly discussed. Recent advances in the chemistry of bulky bisphosphane ligands related to the dppf motif are summarized in this review covering the literature from 1981 to 2020 related to over 220 original references. Besides synthetic aspects outlining the synthesis of such compounds, structural features are discussed along with their implications for the electronic situation and donor properties. Together with the steric situation the latter are combined to elucidate trends in the catalytic performance of such compounds either acting as ligands or on their own merits.
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