Infrared Spectroscopic Characterization of Chromium Carbonyl Species Formed by Ultraviolet Photoreduction of Silica-Supported Chromium(VI) in Carbon Monoxide

Abstract

The molybdenum carbonyl species formed by ultraviolet photoreduction of Mo[sup 6+]SiO[sub 2] in CO were characterized with Fourier transform infrared spectroscopy and temperature-programmed decomposition (TPDE). Mo[sup 6+]SiO[sub 2] samples containing 0.07-6.4% Mo were prepared from MoCl[sub 5], Mo[sub 2]([eta][sup 3]-C[sub 3]H[sub 5])[sub 4], and (NH[sub 4])[sub 6]Mo[sub 7]O[sub 24][center dot]4H[sub 2]O. Four molybdenum carbonyl species have been identified: mer-Mo[sup 4+](CO)[sub 3], cis-Mo[sup 4+](CO)[sub 2], linear Mo[sup 4+](CO), and Mo(CO)[sub 6]. The stoichiometry of photoreduction, decomposition, and reoxidation supports the +4 oxidation state for the mono-, di-, and tricarbonyls. The C[sub 2v] symmetry of mer-Mo(CO)[sub 3] resulted in an IR spectrum consisting of a weak (A[sub 1])[sub 1] symmetric trans C-O stretch at 2181 cm[sup [minus]1], a strong B[sub 2] antisymmetric trans C-O stretch at 2141 cm[sup [minus]1], and a strong (A[sub 1])[sub 2] cis C-O stretch at 2108 cm[sup [minus]1]. The mer-Mo(CO)[sub 3] structure successfully predicted the observed frequencies and intensities of partially substituted Mo([sup 12]C[sup 16]O)[sub x]([sup 13]C[sup 16]O)[sub 3[minus]x] and Mo([sup 12]C[sup 16]O)[sub x]([sup 13]C[sup 18]O)[sub 3[minus]x] (x = 1, 2). Mo(CO)[sub 3] was stable at 300 K with CO partial pressures above 60 Torr. At 193 K, this species was stable under vacuum. Evacuation of mer-Mo(CO)[sub 3] more » at 300 K led to CO ligand loss, resulting in the sequential formation of cis-Mo(CO)[sub 2], linear Mo(CO), and finally, CO-free Mo[sup 4+]. The tricarbonyl assignment is supported by the TPDE pattern, in which two CO ligands were released near 350 K, followed by desorption of the final CO group near 440 K. The stable species are photoformed in the sequence mer-Mo[sup 4+](CO)[sub 3], cis-Mo[sup 4+](CO)[sub 2], and Mo(CO)[sub 6]. 31 refs., 9 figs., 4 tabs. « less