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Abstract: The reaction between 1-boranyl-1,3,5-triaza-7-phosphaadamantane ligand N–B–PTA(BH3) and [Cp∗RhCl(μ-Cl)]2 affords [Cp∗Rh{N–B–PTA(BH3)}Cl2] (3) or [Cp∗Rh{N–B–PTA(BH3)}2Cl]Cl (5) containing one or two P-bonded boronated PTA ligands. The hydride [Cp∗Rh{N–B–PTA(BH3)}H2] (8) was also obtained by reaction of 3 with NaBH4 and alternatively by direct hydroboration of [Cp∗Rh(PTA)Cl2] with excess NaBH4. Moderately slow hydrolysis of the N-boranyl rhodium complexes affords dihydrogen, H3BO3 and the corresponding PTA derivatives, including the water-soluble dihydride [Cp∗Rh(PTA)H2] (9). Finally, the reaction of 8 with electron poor alkynes gives the alkene complexes [Cp∗Rh{N–B–PTA(BH3)}(η2-CH2 =CHR)] (R=Ph, 10; C(O)OEt, 11) as a mixture of rotamers η2-coordinated to rhodium without affecting the N–BH3 moiety. The X-ray crystal structures of 3 and 10 were also obtained and are here discussed. [Copyright &y& Elsevier]