Tuning the redox non-innocence of a phenalenyl ligand toward efficient nickel-assisted catalytic hydrosilylation

Abstract

The hydrosilylation of olefins by a nickel(ii) catalyst assisted by a redox non-innocent phenalenyl (PLY) ligand is reported.

Storing redox equivalent in the phenalenyl backbone towards catalytic multi-electron reduction

“…The successful catalytic reduction of carboxylic acid, which is greatly supported by the redox active delocalized ligand backbone, inspired us to study the mechanistic course of the reaction thoroughly. Our previous finding that the PLY backbone behaves as a redox reservoir and triggers a radical catalyzed reaction, prompted us to examine whether this reduction also adopts a radical pathway 43. In agreement with this hypothesis, we observed that the addition of a radical quencher TEMPO in two equivalents completely shuts down the reaction.…”

“…2b). The close proximity of these reduction potential values to those of previously reported (PLY-O,O) 2 Ni(THF) 2 strongly suggests the reductions are primarily ligand based 43. The Δ E 2–1 value from the voltammogram is –0.24 V, which is also in close agreement to bis-phenalenyl–boron complexes bearing the same phenalenyl based ligand (the Δ E 2–1 values are –0.29 and –0.28 V).…”

An Iron‐Based Long‐Lived Catalyst for Direct C−H Arylation of Arenes and Heteroarenes

“…It may be noted that the same NBMO of phenalenyl based molecules earlier played a key role in designing molecules with several intriguing properties such as organic magnets, conductors, organic spin based electronics, and batteries . Only recently, the use of phenalenyl‐based molecules has been evolving for the design of various catalysts . The topic of phenalenyl‐based molecules to design various catalysts and spin electronic materials was reviewed recently …”

“…[25][26][27][28][29][30][31][32][33][34] Only recently,t he use of phenalenyl-based molecules has been evolving for the design of variousc atalysts. [35][36][37] The topico fp henalenyl-based moleculest od esign variousc atalysts ands pin electronic materials was reviewed recently. [38] We initiatedt he present study by optimizing the reaction conditions for direct CÀHa rylation of thiophene( 2a)w ith para-chlorophenyl diazo-tetrafluoroborate salt (3a)u sing Fe(PLY-O,O) 3 (1)c atalyst (see the Supporting Information, Ta ble S1).…”

Switching between mono and doubly reduced odd alternant hydrocarbon: designing a redox catalyst

“…20 Recently, such in situ generated mono-reduced phenalenyl based radicals were reported in designing cathode materials for single component H 2 O 2 fuel cell 21 and in electron transfer catalysis during various organic transformations. [22][23][24][25] Such approach using in-situ generated mono-reduced phenalenyl radicals opens a possibility to bridge between two seemingly dissimilar areas such as spin-electronics and catalysis. 26…”