A series of metalfbimetal catalysts has been prepared from molecular car-bony1 clusters such as Rh6-yIr, (CO),,(x = 0-6) and Rh,Fe,(CO):, which were synthesized inside NaY zeolite supercages. Nay-entrapped Rh,, Ir, , Rh41r2, Rh,Ir, and Rh,Ir4 crystallites derived from the precursor carbonyl clusters have been well characterized by f.t.i.r., EXAFS, '29Xe n.m.r. and CO/ H chemisorption on their metallic structures and electronic states. The results suggested that the reduced crystallites inside NaY zeolite consist of cluster ensembles < 10 8, in size with controlled metal compositions. These

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Solid-state NMR spectroscopy of 13 C is used to structurally characterize and quantify carbonyl groups in Rh 6 (CO) 16 and Rh + (CO) 2 complexes entrapped in NaY zeolite. MAS NMR line shape simulations show that the dicarbonyl groups present in Rh 6 (CO) 16 and Rh + (CO) 2 have the same shielding parameters (σ iso ∼ 178 ppm, CSA ∼ 400 ppm, and η ∼ 0.2) but exhibit greatly different spin-lattice relaxation rates. Bridged groups exist only in clusters and are bonded to three Rh atoms. Their shielding parameters [σ iso ∼ 251 ppm, CSA ∼ 180 ppm, and negligible anisotropy (η)] differ from bulk Rh 6 (CO) 16 and from those found earlier for CO bridged between two Rh atoms. The Rh 6 :Rh + ratio can be measured directly from the MAS spectra or from the relaxation data. The residual broadening of 150-200 Hz in the MAS spectra is due to distribution of isotropic resonances in the sample. All CO species are immobile at room temperature on the NMR time scale (of the order of a millisecond), whereas slow exchange between dicarbonyls on hexarhodium clusters and isolated rhodium cations was found at 380 K.