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

Journal of the American Chemical Society
Jeremiah D EricksonLawrence F Dahl

Abstract

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.

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Citations

Aug 24, 2016·Chemical Reviews·Michael A BolesDmitri V Talapin
Jun 7, 2017·Chemical Reviews·Indranath Chakraborty, Thalappil Pradeep
Apr 22, 2016·Angewandte Chemie·Tatsuya HigakiRongchao Jin
Feb 22, 2017·Dalton Transactions : an International Journal of Inorganic Chemistry·Zhen LeiQuan-Ming Wang
Jul 1, 2017·Journal of the American Chemical Society·Tatsuya HigakiRongchao Jin
Feb 3, 2018·Chemistry : a European Journal·Shan JinManzhou Zhu
Apr 1, 2016·Chemical Communications : Chem Comm·Lauren E MarbellaJill E Millstone
Aug 12, 2018·Angewandte Chemie·Kerstin MayerRoland A Fischer
Jun 6, 2019·Chemical Communications : Chem Comm·Zhao-Feng WuJing Li
Jan 25, 2017·Dalton Transactions : an International Journal of Inorganic Chemistry·Lei HuangNanfeng Zheng
Jun 12, 2021·Chemical Society Reviews·Max SchützThomas F Fässler
Nov 14, 2020·Small·Mohammad BodiuzzamanThalappil Pradeep
Jun 28, 2019·ACS Nano·Xiangsha Du, Rongchao Jin
Jan 9, 2020·Inorganic Chemistry·Andrew W CookTrevor W Hayton

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