具有拟 Ih 对称性的 Mackay 55 金属原子双壳二十面体 Pd55L12(μ3-CO)20（L = PR3，R = 异丙基）的分离与结构特征：与帽状三壳 Pd145 中内部双壳二十面体、以 Pt 为中心的四壳 Pd-Pt M165 和四壳 Au133 纳米团簇的比较分析。
Isolation and Structural Characterization of a Mackay 55-Metal-Atom Two-Shell Icosahedron of Pseudo-Ih Symmetry, Pd55L12(μ3-CO)20 (L = PR3, R = Isopropyl): Comparative Analysis with Interior Two-Shell Icosahedral Geometries in Capped Three-Shell Pd145, Pt-Centered Four-Shell Pd-Pt M165, and Four-Shell Au133 Nanoclusters.
机构信息
Department of Chemistry, University of Wisconsin-Madison , Madison, Wisconsin 53706, United States.
Center for Integrated Nanotechnologies, Los Alamos National Laboratory , Los Alamos, New Mexico 87545, United States.
出版信息
J Am Chem Soc. 2016 Feb 10;138(5):1502-5. doi: 10.1021/jacs.5b13076. Epub 2016 Jan 31.
We present the first successful isolation and crystallographic characterization of a Mackay 55-metal-atom two-shell icosahedron, Pd55L12(μ3-CO)20 (L = PPr(i)3) (1). Its two-shell icosahedron of pseudo-Ih symmetry (without isopropyl substituents) enables a structural/bonding comparison with interior 55-metal-atom two-shell icosahedral geometries observed within the multi-shell capped 145-metal-atom three-shell Pd145(CO)72(PEt3)30 and 165-metal-atom four-shell Pt-centered (μ12-Pt)Pd164-xPtx(CO)72(PPh3)20 (x ≈ 7) nanoclusters, and within the recently reported four-shell Au133(SC6H4-p-Bu(t))52 nanocluster. DFT calculations carried out on a Pd55(CO)20(PH3)12 model analogue, with triisopropyl phosphine substituents replaced by H atoms, revealed a positive +0.84 e charge for the entire Pd55 core, with a highly positive second-shell Pd42 surface of +1.93 e.
我们首次成功分离并对钯 55 金属原子双壳二十面体 Pd55L12(μ3-CO)20（L = PPr(i)3）（1）进行了晶体学表征。其具有拟 Ih 对称的双壳二十面体（无异丙基取代基），能够与多壳层盖帽的 145 金属原子三壳层 Pd145(CO)72(PEt3)30 和 165 金属原子四壳层以 Pt 为中心的（μ12-Pt）Pd164-xPtx(CO)72(PPh3)20（x ≈ 7）纳米团簇以及最近报道的四壳层 Au133(SC6H4-p-Bu(t))52 纳米团簇内观察到的内部 55 金属原子双壳二十面体几何结构进行结构/键合比较。对具有三异丙基膦取代基被 H 原子取代的 Pd55(CO)20(PH3)12 模型类似物进行的 DFT 计算表明，整个 Pd55 核带正电荷 +0.84 e，高度正的第二壳层 Pd42 表面带正电荷 +1.93 e。
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