A facile approach to the synthesis of diaryl- and dialkyl-substituted monophosphino-o-carboranes by rhodium(I)-catalyzed phosphine-directed B -H activation has been developed for the first time. Upon switching rhodium(I) to palladium(II), C-arylated and B -halogenated products were obtained by using tBuOLi and Li CO as base, respectively. These discoveries provide some simple and efficient approaches to the modification of monophosphino-o-carboranes.
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