The intrazeolite chemistry of the two germylene complexes Cl2CTHF)GeM(CO)5 (M = Mo,
W) was studied with x-ray absorption spectroscopy (Ge, Mo, W edge EXAFS) and in-situ
FTIR/TPD-MS techniques. The slightly decarbonylated GeMo complex interacts with the
framework of NaY zeolite at room temperature and retains the Ge-Mo bond up to about 100° C. In
proton-loaded HY zeolite, framework interactions increase at elevated temperature, and the attached
complex retains the Ge-Mo bond up to about 120° C. The Ge-Mo bond is cleaved at higher
temperatures. MoClx and Mo-Mo species are formed in NaY and HY zeolite, respectively, while
GeClx fragments are anchored to the zeolite framework.
The complex Cl2(THF)GeW(CO)5 retains all five CO ligands up to about 100° C in both
NaY and the proton form. Detectable anchoring occurs at room temperature in NaY and at about
80° C in the proton form. WC1X species are formed upon cleavage of the Ge-W bond at higher
temperatures
