Immobilization of a Soluble Metal Complex in an Organic Network. Remarkable Catalytic Performance of a Porous Dialkoxyzirconium Polyphenoxide as a Functional Organic Zeolite Analogue

摘要: Treatment of anthracenebisresorcinol 1 (a tetraphenol) with Zr(OtBu)4 in THF results polycondensation to give an O−Zr−O network and affords a poly(dialkoxyzirconium phenoxide), 14-·2[Zr(OtBu)2] (Zr host), quantitative yield as insoluble, amorphous, microporous powder particle size ∼0.7 μm, pore nm, specific surface area ∼200 m2/g. The exhibits reversible Langmuir-type adsorption/desorption N2 at 77 K hexane 298 K. Adsorption coadsorption ethyl acetate, benzene, other polar apolar guests also occurs readily Zr host catalyzes the Diels−Alder reaction acrolein 1,3-cyclohexadiene remarkable manner. As solid metal−organic catalyst, it has formula-based turnover rate constant 40 h-1, which far exceeds those its components, i.e., soluble Lewis acid (0.1 h-1) hydrogen-bonded insoluble organic (0.3 h-1). catalyst can be easily separated from product, ...