Metal–organic layers stabilize earth-abundant metal–terpyridine diradical complexes for catalytic C–H activation

Abstract

Metal–organic layers stabilize FeII or CoII-terpyridine diradical complexes to catalyze alkylazide Csp3–H amination and benzylic C–H borylation, respectively.

Structural Engineering of Low‐Dimensional Metal–Organic Frameworks: Synthesis, Properties, and Applications

“…[125] Moreover, 2D MOF nanosheets have been also widely used in catalysis. [59,165,302] Recently, Lin and co-workers reported a series of 2D metal-organic layers, i.e., Fe-TPY/ Zr-BTB MOL, [64] CoCl 2 /Hf-TPY MOL, [178] FeBr 2 /Hf-TPY MOL, [178] which are efficient heterogeneous catalysts for various organic reactions, including hydrosilylation of terminal olefins, CH amination benzylic, CH borylation. [301] Zr-porphyrinic MOF nanosheets with thickness of ≈1.48 nm exhibited excellent photocatalytic performance for the oxidation of 1,5-dihydroxynaphthalene, which is owing to their highly exposed active sites and unique properties of porphyrin units.…”

“…For instance, the Lewis acid centers in Co-BDC nanosheets can catalyze the cycloaddition of CO 2 with epoxides under normal pressure. [64,178] Moreover, catalytically active NPs can be encapsulated within porous frameworks of LD MOFs to achieve enhanced activity and/or selectivity. [79] In addition to directly acting as catalysts, LD MOFs have been also investigated as support materials for the other catalytically active materials.…”

Radical‐Type Reactivity and Catalysis by Single‐Electron Transfer to or from Redox‐Active Ligands

“…[47] This system is at least one order of magnitude morea ctive than all other reporteds ystems to date, all of which operate through metalloradicalc atalysis. [48][49][50][51] The Fe III -complex could be quantitatively recycled and re-used after catalysis. It was established that in situ reduction under the same conditions as for the Pd-system led to Fe-centered rather than ligand-centered reduction, with subsequent disproportionation to afford ac rystallographically characterized homoleptic Fe II (L1 ISQ ) 2 complex that was completely inactive for the CÀHa mination reaction.…”

2D Metal–Organic Frameworks as Multifunctional Materials in Heterogeneous Catalysis and Electro/Photocatalysis

“…In another example, CoCl 2 ·TPY‐MOL was analogously prepared and its catalytic activity tested in the benzylic C–H borylation of methylarenes using B 2 pin 2 ( Scheme ) . CoCl 2 ·TPY‐MOL was activated with NaEt 3 BH, promoting m ‐xylene borylation in 42% yield with a 4.2:1 selectivity toward the benzylic position.…”