Song Yang, Huang Tao, Murray Royce W
Kenan Laboratories of Chemistry, University of North Carolina, Chapel Hill, North Carolina, 27599-3290, USA.
J Am Chem Soc. 2003 Sep 24;125(38):11694-701. doi: 10.1021/ja0355731.
This paper describes reactions in which ligands are exchanged and metals are transferred between monolayer-protected metal clusters (MPCs) that are in different phases (heterophase exchange) or are in the same phase. For example, contact of toluene solutions of alkanethiolate-coated gold MPCs with aqueous solutions of tiopronin-coated gold MPCs yields toluene-phase MPCs that have some tiopronin ligands and aqueous-phase MPCs that have some alkanethiolate ligands. In a second example, heterophase transfer reactions occur between toluene solutions of alkanethiolate-coated gold MPCs and aqueous solutions of tiopronin-coated silver MPCs, in which tiopronin ligands are transferred to the former and gold metal to the latter phase. These ligand and metal exchange reactions are inhibited when conducted under N(2). The results implicate participation of an oxidized form of Au (such as a Au(I) thiolate, Au(I)-SR) as both a ligand and metal carrier in the exchange reactions. Au(I)-SR is demonstrated to be an exchange catalyst.
本文描述了配体发生交换以及金属在处于不同相（异相交换）或相同相的单层保护金属簇（MPC）之间转移的反应。例如，烷硫醇盐包覆的金MPC的甲苯溶液与硫普罗宁包覆的金MPC的水溶液接触，会产生含有一些硫普罗宁配体的甲苯相MPC和含有一些烷硫醇盐配体的水相MPC。在第二个例子中，烷硫醇盐包覆的金MPC的甲苯溶液与硫普罗宁包覆的银MPC的水溶液之间会发生异相转移反应，其中硫普罗宁配体转移到前者，金金属转移到后者相中。这些配体和金属交换反应在氮气气氛下进行时会受到抑制。结果表明，金的氧化形式（如硫醇金（I），Au（I）-SR）作为配体和金属载体参与了交换反应。已证明Au（I）-SR是一种交换催化剂。
