快速交流：金（I）/金（III）催化循环的具有挑战性的计算描述
Flash Communication: Challenging Computational Description of Gold(I)/Gold(III) Catalytic Cycles.
作者信息
Arranz Isabel, Maseras Feliu, Echavarren Antonio M
机构信息
Institute of Chemical Research of Catalonia (ICIQ-CERCA), The Barcelona Institute of Science and Technology, Av. Països Catalans 16, 43007 Tarragona, Spain.
Departament de Química Analítica i Química Orgànica, Universitat Rovira i Virgili, C/Marcel·lí Domingo s/n, 43007 Tarragona, Spain.
出版信息
Organometallics. 2025 Jun 4;44(12):1241-1245. doi: 10.1021/acs.organomet.5c00081. eCollection 2025 Jun 23.
We have investigated the mechanism of cross-coupling reactions catalyzed by gold-(I) complexes without the assistance of chelating ligands. Following pioneering studies by Kochi, gold-(I) complexes with simple alkyl phosphines as ligands are considered. The reaction between cinnamyl bromide and PhSnMe is experimentally shown to take place in the presence of a [MePAuCl] complex. However, our attempt to characterize computationally, using density functional theory (DFT), a mechanism following a plausible gold-(I)/gold-(III) catalytic cycle unearths an unexpectedly complex situation, showing a large range of energy values computed with different functionals.
我们研究了在没有螯合配体协助的情况下，金（I）配合物催化的交叉偶联反应的机理。继高知的开创性研究之后，考虑了以简单烷基膦为配体的金（I）配合物。实验表明，在[MePAuCl]配合物存在下，肉桂基溴与PhSnMe之间会发生反应。然而，我们试图使用密度泛函理论（DFT）对遵循合理的金（I）/金（III）催化循环的机理进行计算表征时，发现了一个出乎意料的复杂情况，即使用不同泛函计算出的能量值范围很大。
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