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The dimeric complex [Rh 2 Cl 2 (CO) 4 ] was grafted to multiwalled carbon nanotubes (MWNTs) previously oxidised with nitric acid and then treated with sodium carbonate to produce carboxylate groups on their outer surface. The grafting mechanism involves bridge-splitting and substitution of -COO for Cl, as evidenced by the presence of NaCl in the samples. A further reduction/decomposition step under dihydrogen at 573 K afforded highly dispersed rhodium nanoparticles (ഠ1.5−2.5 nm). This novel rhodium-supported carbon material (Rh/MWNT-COONa) was tested as a catalyst for the hydrogenation of trans-cinnamaldehyde and the hydroformylation of hex-1-ene in the liquid phase: in both cases it was found to be very selective, toward C=C double-bond hy-

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