Unsymmetrical diaryl selenides were prepared by nucleophilic displacement of chloride with areneselenolates in η6-(arene) Cr(CO)3, FeCpPF6, and Mn(CO)3PF6 complexes. Areneselenolates were conveniently generated in situ by hydrazine reduction of the corresponding diaryl diselenides and reacted with chloroarene Cr(CO)3 complexes in dimethyl sulfoxide at 70 °C. The reactivity of the cationic FeCpPF6 and Mn(CO)3PF6 chloroarene complexes was substantially higher, affording substitution products at ambient temperature in ethanol with areneselenolates generated by sodium borohydride reduction. Intermediate (arylseleno)arene chromium and iron complexes were isolated and characterized by 77Se NMR. As compared with the free diaryl selenide, complexation caused a 20−45 ppm downfield shift.

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