The intrazeolite chemistry of the two germylene complexes Cl2(THF)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. MoC1x 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.