The preparation and characterization of sterically protected diphosphinidenecyclobutenes bearing two two-coordinate phosphorus atoms are described from the viewpoint of the development of a novel type of bidentate ligand for transition-metal complexes. They form complexes with group 6 metals such as chromium, molybdenum and tungsten, group 8 metals such as ruthenium, group 10 metals such as palladium and platinum, and group 11 metals such as copper and gold. Some of them can be used as catalysts for synthetic reactions such as cross-coupling of the Sonogashira type, Suzuki–Miyaura coupling, Ullmann coupling, Kosugi–Migita–Stille coupling, cyanation, polymerization of ethylene, dehydrogenative hydrosilylation of ketones, hydroamination of 1,3-butadienes, and direct alkylation or amination of allylic alcohols of Tsuji–Trost reactions.
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