A recyclable rhodium catalyst anchored onto a bipyridine covalent triazine framework for transfer hydrogenation of N-heteroarenes in water

Abstract

Covalent triazine frameworks (CTFs) based on polydentate ligands are highly promising supports to coordinate well-defined active metal complexes, hereby combining the well-known reactivity of homogeneous catalysts with the robustness and...

Pyrene‐ and Bipyridine‐based Covalent Triazine Framework as Versatile Platform for Photocatalytic Solar Fuels Production**

“…Compared to pristine Py‐CTF‐Bpy the apparent surface area is slightly reduced (190 m 2 /g instead of 270 m 2 /g, Figure S10) as is the thermal stability (Figure S13, for further characterization see SI section 3). The results are in line with a recent report from Stevens and co‐workers on the RhCp* functionalization of bpyCTF obtained by the ionothermal synthesis pathway [54] …”

“…The results are in line with a recent report from Stevens and co-workers on the RhCp* functionalization of bpyCTF obtained by the ionothermal synthesis pathway. [54] Amongst well-defined molecular catalysts that allow the photoinduced selective transformation of CO 2 into formic acid, the Cp*Rh(bpy) complex stands out by its high catalytic activity and selectivity. [2,55] The catalytic activity was evaluated in a solution of acetonitrile (ACN) containing TEOA as base and 1,3dimethyl-2-phenyl-2,3-dihydro-1H-benzo[d]imidazole (BIH) as sacrificial electron donor under visible light irradiation using a solar simulator.…”

Unravelling the Molecular Structure and Confining Environment of an Organometallic Catalyst Heterogenized within Amorphous Porous Polymers**

“…Recently, we have reported heterogeneous rhodium III pentamethylcyclopentadienyl (Cp*Rh) catalysts within bipyridine containing POPs, namely Cp*Rh@BpyMP-1 (Figure 1), that showed very promising results in the selective CO 2 -to-HCOOH photoreduction and transfer hydrogenation reaction. [22,23] Despite the wide use of the Cp*Rh catalytic unit within porous frameworks, [18,22,31,[23][24][25][26][27][28][29][30] its exact molecular structure, positioning and accessibility have remained unexplored due to the particularly challenging structural determination when immobilized in amorphous solids. In particular, the molecular arrangement of the catalyst, including its possible distortion when confined in a micropore and the distances and nature of the interactions between the outer ligand sphere of the catalyst and the pore wall, has never been explored in detail.…”

Aufklärung der molekularen Struktur und des Confinements eines in amorphen porösen Polymeren heterogenisierten metallorganischen Katalysators**

“…Dieser Katalysator zeigt vielversprechende Aktivitäten in der selektiven CO 2 -zu-HCOOH Photoreduktion sowie in Transferhydrierungsreaktionen. [22,23] Obwohl die katalytisch aktive Cp*Rh Einheit in einer Vielzahl von porösen Netzwerken eingesetzt wird, [18,22,31,[23][24][25][26][27][28][29][30] [23] Katalysators, einschließlich einer möglichen Verzerrung, die durch das Confinement in der Mikropore des Wirtsgitters bedingt ist, sowie die Abstände und Art der Wechselwirkungen zwischen der äußeren Ligandensphäre des Katalysators und der Porenwand, wurden nie im Detail untersucht.…”