Synthesis and Catalytic Hydrogenation Reactivity of a Chromium Catecholate Porous Organic Polymer

Abstract

A single-site chromium catecholate POP (catPOP A 2 B 1 ) was synthesized and characterized via AT-IR, XAS, and EPR spectroscopy. The well-defined, fourcoordinate, 11-electron Cr(III) centers bound to catecholate POP were demonstrated to be active hydrogenation catalysts for nonpolar unsaturated organic substrates under mild conditions (5 mol % of Cr, 200 psi of H 2 , 60 °C). This material constitutes the first example of a well-defined, supported organometallic chromium hydrogenation precatalyst.

Stabilization of reactive Co 4 O 4 cubane oxygen-evolution catalysts within porous frameworks

“…The as-synthesized networks lack long-range periodicity, as evidenced by the absence of sharp Bragg diffraction peaks in the powder X-ray diffraction pattern. It is important to note that crystallinity is not needed for the purpose of obtaining a tunable, porous material that immobilizes the [Co 4 O 4 ] unit (54)(55)(56)(57)(58)(59). To confirm that the cubane clusters survived the synthesis process and were incorporated into the coordination compounds we turned to two local structural methods, atomic pair distribution function (PDF) analysis of X-ray diffraction and Fourier-transform extended X-ray absorption fine structure (FT-EXAFS) analysis, that give structural information in the absence of crystalline long-range order (54).…”

Porous Organic Polymers Containing Active Metal Centers as Catalysts for Synthetic Organic Chemistry

“…43 The Co2(CO)8-mediated polymerization reaction of 2,3-(ethoxymethylenedioxy)-1,4-diethynylbenzene (A) and tetrakis(4-ethynylphenyl)methane (B) is the foundation of various catalysts reported in literature. 44,45,46,47,48,49,50,51 The catechol-POP is capable of coordinating to a large variety of different metals, including Ta 44 , La 45 , and Al 49 .…”

Immobilization of an Iridium Pincer Complex in a Microporous Polymer for Application in Room‐Temperature Gas Phase Catalysis

“…If organometallic species could be grafted on such a MPN, this would ensure homogeneous distribution of a single‐site catalyst over the entire surface area of a non‐functional and inert organic polymer, thus a truly “innocent” support. Such kind of materials have been reported to be active in catalysis application in condensed phase, [29–49] but rarely in gas phase [50] …”