Borane reagents are widely used as reductants for the generation of colloidal metals. When treated with a variety of heterogeneous catalysts such as colloidal Rh, Rh/Al2O3, and Rh(0) black, BH(3)center dot THF (THF = tetrahydrofuran) was found to generate H-2 gas with the concomitant formation of a passivating boron layer on the surface of the Rh metal, thereby acting as a poison and rendering the catalyst inactive toward the dehydrocoupling of Me2NH center dot BH3. Analogous poisoning effects were also detected for (i) colloidal Rh treated with other species containing B-H bonds such as [HB-NH](3), or Ga-H bonds such as those present in GaH(3)center dot OEt2, (ii) colloidal Rh that was generated from Rh(I) and Rh(III) salts using borane or borohydrides as reductants, and (iii) for other metals such as Ru and Pd. In contrast, analogous poisoning effects were not detected for the catalytic hydrogenation of cyclohexene using Rh/Al2O3 or the Pd-catalyzed Suzuki cross-coupling of PhB(OH)(2) and PhI. These results suggest that although this poisoning behavior is not a universal phenomenon, the observation that such boron layers are formed and surface passivation may exist needs to be carefully considered when borane reagents are used for the generation of metal colloids for catalytic or materials science applications.