C–H Arylation of Benzene with Aryl Halides using H₂ and a Water‐Soluble Rh‐Based Electron Storage Catalyst

Abstract

This paper reports the first example of CÀ H arylation of benzene under mild conditions, using H 2 as an electron source {turnover numbers (TONs) = 0.7-2.0 for 24 h}. The reaction depends on a Rh-based electron storage catalyst, and proceeds at room temperature and in aqueous solution. Furthermore, the H 2 is inactive during the radical transfer step, greatly reducing unwanted side reactions.

Safe, One-Pot, Homogeneous Direct Synthesis of H2O2

“…We characterized this complex by UV–vis–NIR absorption spectroscopy (Figure S9), XPS (Figure S8a), 1 H NMR spectroscopy (Figure S10), and elemental analysis. A UV–vis–NIR absorption spectrum of 2 shows a broad absorption band at 650–1000 nm with/without CH 3 COONa (Figure S9), which is likely to arise from a charge transfer band, derived from metal–metal interactions, as seen in Rh I polypyridyl complexes. − An XPS spectrum of 2 shows Rh 3d 3/2 and 3d 5/2 peaks at 312.2 and 307.5 eV, respectively (Figure S8a). These binding energies were lower than those of Rh II complex 1 (313.3 and 308.7 eV) (Figure S8c), but similar to those of the reported Rh I complexes. ,− Since the O 2 -sensitive 2 could not be crystallized, its structure was confirmed by X-ray analysis as a CO-adduct of 2 , [Rh I (L)­(CO)]­(NO 3 ) {[ 5 ]­(NO 3 )} (Figure S11).…”

Storing electrons from H2 for transfer to CO2, all at room temperature

“…H 2 ase is an enzyme that activates H 2 as an energy source at room temperature, 10,11 and we have made a series of model compounds that mimic such behavior. [12][13][14][15][16][17][18][19] This has led us to produce potential H 2 -derived energy carriers (H 2 ECs) with all the requirements.…”

“…The extraction of the electron from H 2 has been performed at room temperature by using hydrogenase model complexes (Table S2, ESI †). [12][13][14]16,18,19,[23][24][25][26] Although the extracted electrons have been used for the reduction of the ferrocenium ion, Cu II , O 2 or organic halides at room temperature, there was no example of the reduction of CO 2 at room temperature (Table S2, ESI †).…”