Insertion of a Hydride Ion Into a Tetrasilver(I) Cluster Covered by S-Donating Rhodium(III) Metalloligands
Insertion of a Hydride Ion Into a Tetrasilver(I) Cluster Covered by S-Donating Rhodium(III) Metalloligands
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DOI：
10.1021/acs.inorgchem.0c03267
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发表时间：
2021-01-04
影响因子：
4.6
通讯作者：
Konno, Takumi
中科院分区：
文献类型：
--
作者：
Fukuda, Yosuke;Yoshinari, Nobuto;Konno, Takumi
本文报道了一个四面体银（I）簇{Ag-4}（4+）被Delta-[Rh（L-cys）（3）]（3-）（L-H（2）cys = L-cysteine）所覆盖，并通过H-离子的引入转化为{Ag 4 H}（3+）簇。通过Delta-[Rh（L-cys）（3）]（3-）与Ag+的1：1反应，在[Ag-4{Rh（L-cys）（3）}（4）]（8-）（[1]（8-））中得到了一个硫桥Ag-I Rh-4（4）III八核结构，其中四面体{Ag-4}（4+）核由四个Delta-[Rh（L-cys）（3）]（3-）单元通过巯基连接。密度泛函理论计算表明，在[1]（8-）中，{Ag-4}（4+）存在一个超原子轨道作为最低的未占分子轨道，导致在可见光区出现特征性的电荷转移跃迁.用NaBH 4处理[1]（8-）导致H-离子插入，生成具有{Ag 4 H}（3+）核的[Ag 4 H {Rh（L-cys）（3）}（4）]（9-）（[2]（9-）），伴随着[1]（8-）的可见带消失。在[2]（9-）的中心存在一个H-离子是通过H-1 NMR谱确定的，该谱揭示了一个独特的五重五联体信号，来自被四个AgI原子包围的H-离子。[2]（9-）在水溶液中相当稳定，这归因于{Ag-4}（4+）的未占超原子轨道与{Ag-4 H}（3+）核中H-的已占轨道之间的化学键。
Here, we report a tetrahedral silver(I) cluster of {Ag-4}(4+) covered by Delta-[Rh(L-cys)(3)](3-) (L-H(2)cys = L-cysteine), which is converted to an {Ag4H}(3+) cluster via the inclusion of a H- ion. The 1:1 reaction of Delta-[Rh(L-cys)(3)](3-) with Ag+ gave a sulfur-bridged Ag-I Rh-4(4)III octanuclear structure in [Ag-4{Rh(L-cys)(3)}(4)](8-) ([1](8-)), in which a tetrahedral {Ag-4}(4+) core is bound by four Delta-[Rh(L-cys)(3)](3-) units through thiolato groups. DFT calculations revealed that a superatomic orbital exists in {Ag-4}(4+) as the lowest unoccupied molecular orbital, contributing to the appearance of a characteristic charge-transfer transition in the visible region for [1](8-). Treatment of [1](8-) with NaBH4 led to the insertion of a H- ion to generate [Ag4H{Rh(L-cys)(3)}(4)](9-) ([2](9-)) with an {Ag4H}(3+) core, accompanied by the disappearance of the visible band for [1](8-). The presence of a H- ion in the center of [2](9-) was established by the H-1 NMR spectrum, which reveals a unique quintuple-quintet signal from the H- ion surrounded by four AgI atoms. [2](9-) was considerably stable in aqueous media, which is ascribed to a chemical bond between the unoccupied superatomic orbital of {Ag-4}(4+) and the occupied orbital of H- in the {Ag4H}(3+) core.