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Convenient conditions are reported for the preparation of ytterbium(III) chalcogenolate complexes by insertion of ytterbium metal into the chalcogen-chalcogen bond of disulfides, diselenides, and ditellurides. The resulting complexes have been found to transfer arylsulfanyl, -selenanyl, and -telluranyl groups to epoxides in a facile ring-opening reaction. The ytterbium(III) chalcogenolate complexes...