Department of Chemistry, Graduate School of Science , The University of Tokyo , 7-3-1 Hongo , Bunkyo-ku, Tokyo 113-0033 , Japan.
Institute for Molecular Science , Myodaiji, Okazaki 444-8585 , Japan.
J Am Chem Soc. 2019 Sep 11;141(36):14048-14051. doi: 10.1021/jacs.9b06254. Epub 2019 Aug 21.
[PtAu(SCHPh)] () was fully and selectively converted to , having an open electronic structure with seven valence electrons, upon the addition of an equiamount of NaBH. Stoichiometric production of by the reaction between an equal amount of and revealed that the above reaction proceeds via the spontaneous electron transfer (ET) from nascently reduced by H-mediated reduction to remaining in the solution. Theoretical calculation suggested that the driving force of this novel ET reaction was the larger adiabatic electron affinity of compared to that of , partly associated with reduction-induced relief of the Jahn-Teller strain. We propose that ET proceeds via the dimer complex of and formed through the aurophilic interaction between Au(I) sites in the surface layer.
PtAu(SCHPh)在加入等摩尔量的 NaBH 后完全且选择性地转化为，具有开放的电子结构，有七个价电子。通过等摩尔量的和之间的反应来制备，表明上述反应通过 H 介导还原生成的新生还原的从自发电子转移（ET）进行，还原生成的留在溶液中。理论计算表明，这种新型 ET 反应的驱动力是与相比，较大的绝热电子亲合能，部分与还原诱导的 Jahn-Teller 应变松弛有关。我们提出 ET 通过表面层中 Au(I)位点之间的金键相互作用形成的和二聚体复合物进行。
