Metal complexes with an aminosubstituted tricarbollide ligand

The reaction of the tricarbollide salt Tl[7-tBuNH-7,8,9-C3B8H10] (Tl1) with [(cod)Rh(THF)x]+ gives the rhodium complex [1-(cod)-12-tBuNH-1,2,4,12-RhC3B8H10] in almost quantitative yield. Analogous reactions of Tl1 with [(ring)M(THF)x]2+ ((ring)M = Cp*Rh and (1,3,5-C6H3Me3)Ru) afford the corresponding metallatricarbollides [1-(ring)-12-tBuNH-1,2,4,12-MC3B8H10] in ca. 50% yield. Refluxing Tl1 with [Mn(CO)3(MeCN)3]+ in THF give the tricarbollide analogue of cymantrene, [1,1,1-(CO)3-12-tBuNH-1,2,4,12-MnC3B8H10], the structure of which was determined by single-crystal X-ray diffraction analysis. In all cases, the formation of the metallatricarbollide complexes is accompanied by polyhedral rearrangement leading to the maximum separation of the cage carbon atoms.