Stoichiometric Formation of Open-Shell [PtAu24(SC2H4Ph)18]- via Spontaneous Electron Proportionation between [PtAu24(SC2H4Ph)18]2- and [PtAu24(SC2H4Ph)18]0
Stoichiometric Formation of Open-Shell [PtAu24(SC2H4Ph)18]- via Spontaneous Electron Proportionation between [PtAu24(SC2H4Ph)18]2- and [PtAu24(SC2H4Ph)18]0
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DOI：
10.1021/jacs.9b06254
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发表时间：
2019-09-11
影响因子：
15
通讯作者：
Tsukuda, Tatsuya
中科院分区：
文献类型：
--
作者：
Suyama, Megumi;Takano, Shinjiro;Tsukuda, Tatsuya
当加入等量的NaBH 4时，[PtAu 24（SC2 H4 Ph）（18）]（0）（[PtAu 24]（0））完全且选择性地转化为具有七个价电子的开放电子结构的[PtAu 24]（-）。等量的[PtAu_（24）]（0）与[PtAu_（24）]（2-）反应生成[PtAu_（24）]（-）表明，上述反应是通过自发电子转移（ET）从被H ~-还原的[PtAu_（24）]（2-）到残留在溶液中的[PtAu_（24）]（0）进行的。理论计算表明，[PtAu_（24）]（0）的绝热电子亲合势大于[PtAu_（24）]（-）的绝热电子亲合势，这与还原引起的Jahn-Teller应变的释放有关。我们认为ET是通过[PtAu_（24）]（2-）和[PtAu_（24）]（0）的二聚体络合物进行的，该络合物是通过表面层中Au（I）位点之间的亲金作用形成的。
[PtAu24(SC2H4Ph)(18)](0) ( [PtAu24](0)) was fully and selectively converted to [PtAu24](-), having an open electronic structure with seven valence electrons, upon the addition of an equiamount of NaBH4. Stoichiometric production of [PtAu24](-) by the reaction between an equal amount of [PtAu24](0) and [PtAu24](2-) revealed that the above reaction proceeds via the spontaneous electron transfer (ET) from [PtAu24](2-) nascently reduced by H--mediated reduction to [PtAu24](0) remaining in the solution. Theoretical calculation suggested that the driving force of this novel ET reaction was the larger adiabatic electron affinity of [PtAu24](0) compared to that of [PtAu24](-), partly associated with reduction-induced relief of the Jahn-Teller strain. We propose that ET proceeds via the dimer complex of [PtAu24](2-) and [PtAu24](0) formed through the aurophilic interaction between Au(I) sites in the surface layer.