INTRAZEOLITE PHOTOTOPOTAXY - EXAFS ANALYSIS OF PRECURSOR 8(W(CO)6)-NA56Y AND PHOTOOXIDATION PRODUCTS 16(WO3)-NA56Y AND 28(WO3)-NA56Y

The intrazeolite photooxidation chemistry of alpha-cage encapsulated hexacarbonyltungsten(0) in Na56Y with O2, denoted n{W(CO)6}-Na56Y/O2/hv, which has previously been shown to provide a novel synthetic pathway to alpha-cage located tungsten(VI) oxide, denoted n(WO3)-Na56Y, is now the subject of an extended X-ray absorption fine structure (EXAFS) analysis. The EXAFS data of a precursor 8{W(CO)6}Na56Y, which contains on average one W(CO)6 per alpha-cage shows that the W(CO)6 guest maintains its structural integrity with only minor observable perturbations of the skeletal WC and ligand CO bonds compared to those found for the same molecule in the free state. The EXAFS analysis results for the photoxidation products 16(WO3)-Na56Y and 28(WO3)-Na56Y are very similar and display the presence of two terminal tungsten-oxygen bonds (1.75-1.77 angstrom) and two bridging tungsten-oxide bonds (1.94-1.95 angstrom), together with a short distance to a second tungsten (3.24-3.30 angstrom). This bond length and coordination number information for n = 16 and 28 samples is best interpreted in terms of the formation of a single kind of tungsten trioxide dimer unit (WO3)2, most likely interacting with extraframework Na+ cations, denoted ZONa...O2W(mu-O)2WO2...NaOZ. In conjunction with earlier chemical and spectroscopic information on this system, the EXAFS data support the contention that 16(WO3)-Na56Y contains a uniform array of single size and shape tungsten (VI) oxide dimers (WO3)2 housed in the 13-angstrom supercages of the zeolite Y host. The sequential addition of WO3 units to the 16(WO3)-Na56Y sample appears to increase the (WO3)2 dimer population, causing a buildup of alpha-cage encapsulated dimers-of-dimers {(WO3)2}2 rather than further cluster growth to trimers (WO3)2 and/or tetramers (WO3)4.