Various (arene)tricarbonylchromium complexes were synthesized within the confines of NaX zeolite and studied with diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and carbon-13 magic-angle-spinning nuclear magnetic resonance (MAS NMR) spectroscopy. In each case, the surface complex Cr(CO)3(Oz)3 (Oz represents a framework oxygen of the NaX zeolite) was prepared before a particular arene was added. The arenes benzene, toluene, mesitylene, anisole, and aniline all produce hexahapto pi-complexes physisorbed within the zeolite supercage. DRIFTS spectra show three bands in the carbonyl region indicating less than C3v symmetry. The NMR spectra have narrow carbonyl bands near 240 ppm which indicate rapidly reorienting complexes within the zeolite. The (eta 6-benzene)tricarbonylchromium complex is physisorbed at two sites as indicated both by the DRIFTS spectra and by two carbonyl resonances at 242.5 and 239.1 ppm at 300 K. Variable-temperature MAS NMR shows these two resonances coalescing near 360 K with an activation energy of 48 +/- 6 kJ/mol. When the temperature is decreased to 205 K, the high-frequency carbonyl resonance disappears. The 239 ppm resonance is still narrow at 134 K while MAS sidebands show that the resonance from physisorbed benzene is ca. 200 ppm wide. The complex prepared with pyridine gave a broad resonance as indicated by the spinning sidebands in the MAS NMR spectra. The pyridine complex was identified as Cr(CO)3(C5H5N)3.