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• W4367055144 abstract "The mechanism of the N–N cross-coupling of nitroarene and aniline catalyzed by 1,2,2,3,4,4-hexamethylphosphetane oxide (1PO) as well as the prediction of a better catalyst was theoretically investigated using DFT and DLPNO-CCSD(T) calculations. An active species 1P is generated through deoxygenation of 1PO by diphenylsilane. Then, 1P extracts one oxygen atom from nitroarene to produce nitrosoarene. In this deoxygenation step, the [3 + 1] cheletropic addition is a rate-determining step with the ΔG0≠ and ΔG0 values of 28.8 and −7.3 kcal/mol, respectively. Next, nitrosoarene exclusively undergoes a dehydrative condensation reaction with aniline to form an azo-cation intermediate, which is the origin of the high selectivity in this cross-coupling reaction. In this step, 2,4,6-trimethylbenzoic acid plays an essential role to significantly reduce the ΔG0≠ value from 41.1 to 14.8 kcal/mol. Subsequently, 1P reacts with the azo cation to form a stable hydrazinylphosphonium species through the nucleophilic attack of the phosphorus atom to the cationic nitrogen atom. The phosphonium center preferably accepts a hydroxyl group from water to ensure the formation of hydrazine in the subsequent step. In the [3 + 1] cheletropic addition step, the highest occupied molecular orbital (HOMO) of 1P plays an important role. The small-ring scaffold of 1P raises the HOMO energy compared to acyclic phosphorus compounds to achieve high activity of 1P. Substitution of a dimethylamino group for the methyl group in 1P was theoretically predicted to improve the activity by further increasing the HOMO energy." @default.
• W4367055144 created "2023-04-27" @default.
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• W4367055144 date "2023-04-26" @default.
• W4367055144 modified "2023-09-30" @default.
• W4367055144 title "N–N Bond Formation by a Small-Ring Phosphine Catalyst via the P^III/P^V Cycle: Mechanistic Study and Guidelines to Obtain a Good Catalyst" @default.
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• W4367055144 doi "https://doi.org/10.1021/acscatal.3c01049" @default.
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