包封线性二氢化钯单元的富铜双金属纳米团簇的合成
Synthesis of Bimetallic Copper-Rich Nanoclusters Encapsulating a Linear Palladium Dihydride Unit.
作者信息
Chakrahari Kiran Kumarvarma, Silalahi Rhone P Brocha, Chiu Tzu-Hao, Wang Xiaoping, Azrou Nadia, Kahlal Samia, Liu Yu-Chiao, Chiang Ming-Hsi, Saillard Jean-Yves, Liu C W
机构信息
Department of Chemistry, National Dong Hwa University, No. 1, Sec. 2, Da Hsueh Rd., Shoufeng, Hualien, 97401, Taiwan R.O.C.
Department of Chemistry, SRM Institute of Science and Technology, Kattankulathur, 603203, India.
出版信息
Angew Chem Int Ed Engl. 2019 Apr 1;58(15):4943-4947. doi: 10.1002/anie.201814264. Epub 2019 Mar 13.
The structurally precise Cu-rich hydride nanoclusters [PdCu H (dtc/dtp) (C≡CPh) ] (dtc: di-butyldithiocarbamate (1); dtp: di-isopropyl dithiophosphate (2)) were synthesized from the reaction of polyhydrido copper clusters [Cu H (S CN Bu ) ] or [Cu H {S P(O Pr) } ] with phenyl acetylene in the presence of Pd(PPh ) Cl . Their structures and compositions were determined by single-crystal X-ray diffraction and the results supported by ESI-mass spectrometry. Hydride positions in 1 were confirmed by single-crystal neutron diffraction. Each hydride is connected to one Pd and four Cu atoms in slightly distorted trigonalbipyramidal geometry. The anatomies of clusters 1 and 2 are very similar and DFT calculations allow rationalizing the interactions between the encapsulated [PdH ] unit and its Cu bicapped icosahedral cage. As a result, Pd has the highest coordination number (14) so far recorded.
结构精确的富铜氢化物纳米团簇[PdCuH(dtc/dtp)(C≡CPh)]（dtc：二丁基二硫代氨基甲酸盐(1)；dtp：二异丙基二硫代磷酸酯(2)）由多氢铜团簇[CuH(SCNBu)]或[CuH{S P(O Pr)}]与苯乙炔在Pd(PPh)Cl存在下反应合成。通过单晶X射线衍射确定其结构和组成，并通过电喷雾电离质谱法（ESI - 质谱）对结果进行了验证。通过单晶中子衍射确定了1中氢化物的位置。每个氢化物以略微扭曲的三角双锥几何结构与一个钯原子和四个铜原子相连。团簇1和2的结构非常相似，密度泛函理论（DFT）计算有助于解释被封装的[PdH]单元与其铜双帽二十面体笼之间的相互作用。结果表明，钯具有迄今为止记录到的最高配位数（14）。
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