Hydrazobenzene

Tetrahydrofuran, diethyl ether, hexane, fluorobenzene, and pentane were purchased from Fisher Scientific. The solvents were sparged for 20 min with dry N₂ and dried using a commercial two-column solvent purification system comprising columns packed with Q5 reactant and neutral alumina respectively (for hexane and pentane), or two columns of neutral alumina (for THF, diethyl ether, and fluorobenzene). Pyridine, also purchased from Fisher Scientific, was freeze–pump–thawed for 4 cycles and stored over 4 Å molecular sieves for three days before use. Deuterated solvents were purchased from Cambridge Isotope Laboratories, Inc. Pyridine-d₅ was stored over 4 Å molecular sieves for three days before use, and benzene-d₆ was dried and stored over potassium for 2 days before use. Ce[N(SiMe₃)₂]₃ 93 and Ce[N(SiHMe₂)₂]₄ 88 ,89 (link) were prepared following published procedures. Li[N(SiMe₃)₂] (Acros) was recrystallized from hot pentane prior to use. K[N(SiMe₃)₂] (Acros) and Na[N(SiMe₃)₂] (Acros) were used as purchased. Hydrazobenzene (Sigma Aldrich, MP Biochemicals, Alfa Aesar) was sublimed under reduced pressure first at 60 °C to remove azobenzene, and then at 105 °C for further purification prior to use. Alternatively, the Hydrazobenzene was purified by fractional recrystallization of Hydrazobenzene dissolved in toluene and layered with pentane.

Oleylamine (technical grade, 70%), tungsten(vi) chloride (WCl₆, ≥99.9%, trace metal basis), hexamethyldisilazane (HMDS, reagent grade, ≥99%), carbon disulfide (CS₂, ≥99.9%, anhydrous), tetrahydrofuran (THF, anhydrous, contains 250 ppm BHT as inhibitor, ≥99%), azobenzene (98%), 4-nitrobenzamide (98%), 4-nitrobenzenesulfonamide (97%), 4′-fluoro-3′-nitroacetophenone (97%), 3-nitrostyrene (96%), hydrazobenzene, 1-bromo-4-nitrobenzene (99%), ethyl 4-nitrocinnamate (predominately trans, 99%), 4′-aminoacetophenone (99%), 3-vinylaniline (contains KOH as inhibitor, 97%), 4-nitrothioanisole (96%), 1-chloro-4-nitrobenzene (99%), 1-iodo-4-nitrobenzene (98%), tetradecane (≥99%), nitrosobenzene (≥97%), 3-ethylaniline (98%), p-toluidine (99%), 4-(4-nitrobenzyl)pyridine (98%), 4-nitrobenzonitrile (97%), hydroxylamine hydrochloride (99%), azoxybenzene, and nitrobenzene (99%) were purchased from Sigma Aldrich. Oleic acid (technical grade, 90%) and 4-nitrobenzoic acid (99%) were purchased from Alfa Aesar. Methyl 4-nitrobenzoate (≥98.0%) and 4-nitrobenzaldehyde (≥98.0%) were purchased from TCI. 10% Pt on activated carbon powder was purchased from Premetek. Solvents, including hexane and isopropanol, were of analytical grade. All chemicals were used as received without further purification.