Efficient and Selective Conversion of Phosphine-Protected (MAu8)2+ (M = Pd, Pt) Superatoms to Thiolate-Protected (MAu12)6+ or Alkynyl-Protected (MAu12)4+ Superatoms via Hydride Doping
Efficient and Selective Conversion of Phosphine-Protected (MAu8)2+ (M = Pd, Pt) Superatoms to Thiolate-Protected (MAu12)6+ or Alkynyl-Protected (MAu12)4+ Superatoms via Hydride Doping
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DOI：
10.1021/jacs.9b08055
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发表时间：
2019-10-09
影响因子：
15
通讯作者：
Tsukuda, Tatsuya
中科院分区：
文献类型：
--
作者：
Takano, Shinjiro;Ito, Shun;Tsukuda, Tatsuya
通过氢化物掺杂活化的准球形超原子[HMAu 8（PPh 3）（8）]（+）与Au（I）L齐聚物反应，发展了一种高效、高选择性的合成双金属簇合物MAu 24 L 18（M = Pd或Pt; L =硫醇盐或炔基）的方法.这种双金属离子介导的转化以类似于200 mg规模提供了先前已知的具有二十面体（M@Au-12）（6+）核的簇MAu 24（SC 2 H4 Ph）（18），产率> 50%，并且以良好的产率成功地应用于各种伯硫醇。虽然在仲硫醇盐和叔硫醇盐中的应用受到限制，但转化产生了具有不对称的扁平（Pd@Au-12）（6+）核的新型簇合物[PdAu 23（ScC 6 H 11）（17）]（0）。该转化产生了具有二十面体（M@Au-12）（4+）核的新的炔基保护的簇合物[MAu 24（C（math）CArF）（18）]（2-）（Ar-F = 3，5-（CF 3）（2）C6 H3），产率> 50%。炔基保护的M@Au-12核中的价电子数较多，这是由于炔基比硫醇盐具有更强的吸电子性质，从而增加了M@Au-12核的吸引势.这种简单而通用的自下而上的方法将为大规模合成各种超原子提供机会，以促进以超原子为构建单元的材料科学的发展。
An efficient and selective method was developed for the synthesis of bimetallic clusters, MAu24L18 (M = Pd or Pt; L = thiolates or alkynyls), by the reaction of Au(I)L oligomers with quasi-spherical superatoms [HMAu8(PPh3)(8)](+) activated by hydride doping. This hydride-mediated conversion afforded previously known clusters MAu24(SC2H4Ph)(18) having an icosahedral (M@Au-12)(6+) core at similar to 200 mg scale, with a yield of >50%, and was successfully applied to a variety of primary thiols with good yields. Although the application to secondary and tertiary thiolates was limited, the conversion produced the novel cluster [PdAu23(ScC6H11)(17)](0) having a poorly symmetrical, flattened (Pd@Au-12)(6+) core. The conversion produced the new alkynyl-protected clusters [MAu24(C (math)CArF)(18)](2-) (Ar-F = 3,5-(CF3)(2)C6H3) having an icosahedral (M@Au-12)(4+) core, with a yield of >50%. The larger number of valence electrons in the M@Au-12 core protected by alkynyls is ascribed to an increase in attractive potential of the M@Au-12 core owing to the stronger electron-withdrawing nature of alkynyls than thiolates. This simple and versatile bottom-up approach will provide an opportunity to synthesize a variety of superatoms on a large scale for the promotion of materials science based on superatoms as building units.