The exploitation of metallacarboranes’ potential in various fields of research and practical applications requires the availability of convenient and versatile methods for their functionalization with various functional moieties and/or linkers of different types and lengths. Herein, we report a study on cobalt bis(1,2-dicarbollide) functionalization at 8,8′-boron atoms with different hetero-bifunctional moieties possessing a protected hydroxyl function allowing further modification after deprotection. Moreover, an approach to the synthesis of three and four functionalized metallacarboranes, at boron and carbon atoms simultaneously via additional functionalization at carbon to obtain derivatives carrying three or four rationally oriented and distinct reactive surfaces, is described.

The exploitation of the metallacarboranes’ potential in various fields of research and practical ap-plications requires the availability of convenient and versatile methods for their functionalization with various functional moieties and/or linkers of different types and lengths. Herein we report a study on cobalt bis(1,2-dicarbollide) functionalization at 8,8’-boron atoms with different het-ero-bifunctional moieties containing protected hydroxyl function allowing further modification after deprotection. Moreover, an approach to the synthesis of three and four functionalized metallacarboranes, at boron and carbon atoms simultaneously, via additional functionalization at carbon to obtain derivatives carrying three or four rationally oriented and distinct reactive surfaces, is described